Organic hydroperoxide reduction in perfumery raw materials

ABSTRACT

The aspects presented herein provide methods and compositions for the reduction of the peroxide value of perfume ingredients, formulated perfumes, formulated body care products, formulated skin care products, formulated homecare products, essential oils, food raw materials, formulated food products, and natural extracts.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation of International PatentApplication Serial No. PCT/EP2018/061468, filed on May 4, 2018, andclaims priority to U.S. Provisional Patent Application Ser. No.62/502,156, filed on May 5, 2017, and European Patent Application SerialNo. 17176476.4, filed on Jun. 16, 2017, the entire contents of which arehereby incorporated by reference in their entirety.

FIELD

The various aspects presented herein relate to methods and compositionsfor the reduction of the peroxide value of perfume ingredients,formulated perfumes, formulated body care products, formulated skin careproducts, formulated homecare products, essential oils, food rawmaterials, formulated food products, and natural extracts.

BACKGROUND

Many formulated perfumes, body care products, home care products,perfumery raw materials (such as, for example, essential oils, naturalextracts, and synthetic ingredients), and food raw materials (such as,for example, fats and oils derived from animal or plant sources, andderivatives thereof, including monoglycerides, diglycerides, lecithins,phosphatidyl ethanolamines, or other phospholipids, and modifiedtriglycerides) can undergo oxidation, resulting in the formation ofchemical species including peroxides, organic hydroperoxides,peroxyhemiacetals.

The peroxide value (POV), defined as the amount of equivalents ofoxidizing potential per 1 kilogram of material is an indication of theextent of the oxidation. The POV of formulated perfumes, body careproducts, and perfumery raw materials is, or may be subject toregulatory limits, due to skin sensitization issues, such as, forexample, contact dermatitis. For example, an unacceptably high POV canresult in a perfumery raw material failing quality control testing, andtherefore being deemed unusable. In another example, an unacceptablyhigh POV can result in a food raw material having an unpleasant rancidtaste.

Consequently, there is a need to reduce the incidence of formulatedperfumes, body care products and perfumery raw materials failing qualitycontrol testing, or, causing skin irritation, by reducing the POV in theformulated perfumes, body care products, home care products, cosmeticproducts, and perfumery raw materials. In addition, there is a need toreduce the occurrence of a rancid taste in food raw materials, byreducing the POV in the food raw materials.

SUMMARY

One aspect presented herein, provides a method for reducing the POV of aformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material,comprising the steps of: adding an α-oxocarboxylic acid to theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialhaving a first POV level; and mixing the α-oxocarboxylic acid into theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialfor a time sufficient to reduce the first POV level to a pre-determinedsecond lower level.

One aspect presented herein, provides a method for reducing, preventing,or ameliorating formulated perfume, body care product, homecare product,cosmetic product, or perfumery raw material-induced skin irritation of asubject in need thereof, comprising the steps of: (a) adding anα-oxocarboxylic acid to the formulated perfume, body care product,homecare product, cosmetic product, or perfumery raw material having afirst POV level; and (b) mixing the α-oxocarboxylic acid into theformulated perfume, body care product, homecare product, cosmeticproduct, or perfumery raw material for a time sufficient to reduce thefirst POV level to a pre-determined second lower level, wherein thepre-determined second lower level is sufficient to reduce, prevent, orameliorate the formulated perfume, body care product, homecare product,cosmetic product, or perfumery raw material-induced skin irritation ofthe subject.

In one aspect the perfumery raw material is selected from the groupconsisting of a synthetic ingredient, a natural product, an essentialoil, and a natural extract.

In one aspect, the body care product is a skin cream.

In one aspect, the food raw material is selected from the groupconsisting of a fat, an oil, or a derivative thereof.

In one aspect, the derivative thereof is selected from the groupconsisting of a monoglyceride, a diglyceride, and a phospholipid.

In one aspect, the phospholipid is selected from the group consisting ofa lecithin, a phosphatidyl ethanolamine, and a modified triglyceride.

In one aspect, the perfumery raw material is treated prior to theincorporation into a perfume.

In one aspect, the perfumery raw material is treated after theincorporation into a perfume.

In one aspect, the food raw material is treated prior to theincorporation into a flavored article.

In one aspect the food raw material is incorporated after theincorporation into a flavored article.

In one aspect, the concentration of the α-oxocarboxylic acid ranges from0.001 to 10 weight percent, after the addition to the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material.

In one aspect, the α-oxocarboxylic acid is selected from the groupconsisting of: pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid,2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid,α-ketoglutaric acid, 2-oxopentandioate, indole-3-pyruvic acid,2-thiopheneglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid,4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid, andmixtures thereof.

In one aspect, the perfumery raw material is citrus oil.

In one aspect, the food raw material is a cooking oil.

In one aspect, the pre-determined second lower level is between 5 and 20mmol/L.

In one aspect, the pre-determined second lower level is between 0 and 6mmol/L.

In one aspect, the method further comprises removing the excessα-oxocarboxylic acid from the formulated perfume, body care product,cosmetic product, homecare product, perfumery raw material, flavoredarticle, or food raw material having the pre-determined second lower POVlevel.

In one aspect, the excess α-oxocarboxylic acid is removed from theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialvia a liquid-liquid extraction.

In one aspect, the method further comprises treating the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material afterremoving the α-oxocarboxylic acid to reduce the acidity of theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material.

In one aspect, the formulated perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material is treated with a carbonate salt to reduce the acidityof the formulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material.

One aspect presented herein, provides a composition comprising: (a) aformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material,and (b) an α-oxocarboxylic acid, wherein the α-oxocarboxylic acid ispresent in the composition in an amount sufficient to decrease the POVfrom a first level to a pre-determined second lower level.

One aspect presented herein, provides a composition comprising: (a) aformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material,and (b) an α-oxocarboxylic acid, wherein the α-oxocarboxylic acid ispresent in the composition in an amount sufficient to reduce, prevent,or ameliorate an increase in the POV of the formulated perfume, bodycare product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material.

In one aspect, the α-oxocarboxylic acid is added to the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material at aconcentration ranging from 0.001 to 10 weight percent.

In one aspect, the perfumery raw material is citrus oil.

In one aspect, the α-oxocarboxylic acid is present in the composition inan amount sufficient to prevent the pre-determined second lower levelfrom changing with time.

In one aspect, the concentration of the α-oxocarboxylic acid in thecomposition ranges from 0.001 to 10 weight percent.

In one aspect, the α-oxocarboxylic acid is added to the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material as aninorganic salt.

In one aspect, the α-oxocarboxylic acid is present in the composition asan inorganic salt.

In one aspect the salt is an ammonium salt formed by reacting theα-oxocarboxylic acid with a compound selected from the group consistingof: 2-(dimethylamino)ethanol, N, N-dimethyldodecylamine, Tris[2 (2(methoxyethoxy)ethyl]amine, and N-methyl diethanolamine.

In one aspect, the α-oxocarboxylic acid is added to the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material as a saltof a mono or divalent cation.

In one aspect, the α-oxocarboxylic acid is present in the composition asa salt of a mono or divalent cation.

In one aspect, the α-oxocarboxylic acid is selected from the groupconsisting of: pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid,2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid,α-ketoglutaric acid, 2-oxopentandioate, indole-3-pyruvic acid,2-thiopheneglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid,4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid, andmixtures thereof.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows an exemplar proposed reaction between an α-oxocarboxylicacid and an organic hydroperoxide according to certain aspects presentedherein.

FIG. 2 shows a representation of the rate of reduction of POV in aperfumery raw material according to certain aspects presented herein.

FIG. 3 shows POV of a skin cream by a method according to certainaspects presented herein.

FIG. 4 shows POV of a skin cream by a method according to certainaspects presented herein.

FIG. 5 shows the change in POV of a model perfume treated by a methodaccording to certain aspects presented herein.

FIG. 6 shows the change in POV of a model perfume treated by a methodaccording to certain aspects presented herein.

FIG. 7 shows the POV of a liquid soap formulation treated by a methodaccording to certain aspects presented herein.

FIG. 8 shows the percent reduction in POV of a liquid soap formulationtreated by a method according to certain aspects presented herein.

FIG. 9 shows the POV of a shampoo formulation treated by a methodaccording to certain aspects presented herein.

FIG. 10 shows the percent reduction in POV of a shampoo formulationtreated by a method according to certain aspects presented herein.

FIG. 11 shows the POV of an all-purpose cleaner spray formulationtreated by a method according to certain aspects presented herein.

FIG. 12 shows the percent reduction in POV of an all-purpose cleanerspray formulation treated by a method according to certain aspectspresented herein.

FIG. 13 shows the POV of a skin cream formulation treated by a methodaccording to certain aspects presented herein.

FIG. 14 shows the percent reduction in POV of a skin cream formulationtreated by a method according to certain aspects presented herein.

FIG. 15 shows the POV of an anti-perspirant stick formulation treated bya method according to certain aspects presented herein.

FIG. 16 shows the percent reduction in POV of an anti-perspirant stickformulation treated by a method according to certain aspects presentedherein.

DETAILED DESCRIPTION

In the following description, reference is made to specific embodimentswhich may be practiced, which is shown by way of illustration. Theseembodiments are described in detail to enable those skilled in the artto practice the invention described herein, and it is to be understoodthat other embodiments may be utilized and that logical changes may bemade without departing from the scope of the aspects presented herein.The following description of example embodiments is, therefore, not tobe taken in a limited sense, and the scope of the various aspectspresented herein is defined by the appended claims.

The Abstract is provided to comply with 37 C.F.R. § 1.72(b) to allow thereader to quickly ascertain the nature and gist of the technicaldisclosure. The Abstract is submitted with the understanding that itwill not be used to interpret or limit the scope or meaning of theclaims.

Many formulated perfumes, body care products, homecare products,perfumery raw materials (such as, for example, essential oils, naturalextracts, and synthetic ingredients) can undergo oxidation, resulting inthe formation of chemical species including peroxides, organichydroperoxides, peroxyhemiacetals. In addition, many food raw materials,such as, for example, fats oils, or derivatives thereof, are known toundergo an autoxidation process that results in the formation of theintermediate chemical species glyceride hydroperoxides. The glyceridehydroperoxides may further degrade into aldehydes and ketones. Withoutintending to be limited to any particular theory the autoxidationprocess may result in an unpleasant and unpalatable rancidity of thefood raw material.

The peroxide value (POV), defined as the amount of equivalents ofoxidizing potential per 1 kilogram of material is an indication of theextent of the oxidation. The POV of formulated perfumes, body careproducts, homecare products, cosmetic products, and perfumery rawmaterials is subject to regulatory limits due to skin sensitizationissues, such as, for example, contact dermatitis. For example, anunacceptably high POV can result in a perfumery raw material failingquality control testing, and therefore being deemed unusable. In anotherexample an unacceptably high POV can result in a food raw material, or aformulated food product (also referred to herein as a flavored article)having a rancid taste.

Skin exposure may be the result of an incidental exposure (such as, forexample, of a hard surface cleaner or a hand dishwashing soap when theuser does not wear a pair of gloves when using the product).Alternatively, skin exposure may be the result of a long-term, orintentional exposure (such as, for example, of a shampoo, or skinmoisturizer).

As used herein, the term “peroxide value” or “POV” refers to the amountof equivalents of oxidizing potential per 1 kilogram of material.Without intending to be limited to any particular theory, the POV of amaterial is determined analytically. The term “POV” does not refer to achemical compound or group of compounds, but is often used loosely andinterchangeably with the products of autoxidation within a sample thatcause a response during a POV test. These autoxidation products differdepending upon the particular material being tested. Many classes ofchemical compounds will produce a response during a POV test, includingbut not limited to organic and inorganic hydroperoxides, organic andinorganic peroxides, peroxyhemiacetals, peroxyhemiketals, and hydrogenperoxide itself.

By way of illustration, one POV test is an iodometricoxidation-reduction titration. All POV-responsive compounds share theproperty that they are capable of oxidizing the iodide ion to moleculariodine within the time period specified for the test; in fact, theiodide oxidation reaction is the basis for the test. Thus, “POV” is anumerical value that represents the molar sum total of the all theiodide-oxidizing species in a particular sample.

By way of illustration, limonene and linalool are unsaturated terpenescommonly found as major components in many essential oils. Both limoneneand linalool are easily oxidized by atmospheric oxygen to formhydroperoxides. The hydroperoxides of limonene and linalool are known tobe sensitizers capable of causing contact dermatitis. Consequently,limonene, and natural products containing limonene may only be used asperfumery raw materials when the recommended organic hydroperoxide levelis below 20 mmol/L (or 10 mEq/L). Similarly, essential oils and isolatesderived from the Pinacea family, including Pinus and Abies genera mayonly be used as perfumery raw materials when the recommended organichydroperoxide level is below 10 mmol/L (or 5 mEQ/L).

By way of another illustration, fats oils, or derivatives thereof, areknown to undergo an autoxidation process that leads to unpleasant andunpalatable rancidity. Without intending to be limited to any particulartheory, glyceride hydroperoxides are an intermediate chemical species inthe autoxidation process, which further degrade into aldehydes andketones that produce the rancid aroma.

The POV of a perfumery raw material may be determined by any methodreadily selectable by one of ordinary skill in the art. Non limitingexamples include, iodometric titration, high-performance liquidchromatography, and the like.

An example of a method for determining the POV of a perfumery rawmaterial is disclosed in Calandra et al., Flavour and Fragr. J. (2015),30, p 121-130.

Perfumery raw materials include, but are not limited to essential oils,natural extracts, and synthetic ingredients.

The POV of a formulated perfume, body care product, cosmetic product,homecare product, perfumery raw material, flavored article, or food rawmaterial may be determined by any method readily selectable by one ofordinary skill in the art. No limiting examples include, iodometrictitration, high-performance liquid chromatography, and the like.

An example of a method for determining the POV of a formulated perfumeis disclosed in Calandra et al., Flavour and Fragr. J. (2015), 30, p121-130.

The POV of a formulated body care product may be determined by anymethod readily selectable by one of ordinary skill in the art.Non-limiting examples include iodometric titration, high-performanceliquid chromatography, and the like.

An example of a method for determining the POV of a formulated body careproduct is disclosed in Calandra et al., Flavour and Fragr. J. (2015),30, p 121-130.

Without intending to be limited to any particular theory, the POV of theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialis reduced by treating the formulated perfume, body care product,cosmetic product, homecare product, perfumery raw material, flavoredarticle, or food raw material with an α-oxocarboxylic acid. Theα-oxocarboxylic acid reacts with the organic hydroperoxide via oxidativedecarboxylation, thereby consuming the organic hydroperoxide, reducingthe organic hydroperoxide's oxidative potential. The resulting reactionresults in the oxidation of the α-oxocarboxylic acid to carbon dioxideand the corresponding carboxylic acid containing one less carbon atom,and the reduction of the organic hydroperoxide to its correspondingorganic alcohol. An exemplar proposed reaction, using pyruvic acid asthe α-oxocarboxylic acid and limonene-hydroperoxide as the organichydroperoxide is depicted in FIG. 1.

Accordingly, one aspect presented herein, provides a method for reducingthe POV of a perfumery raw material, comprising the steps of: adding anα-oxocarboxylic acid to the perfumery raw material having a first POVlevel; and mixing the α-oxocarboxylic acid into the perfumery rawmaterial for a time sufficient to reduce the first POV level to apre-determined second lower level.

An alternate aspect presented herein, provides a method for reducing,preventing, or ameliorating perfumery raw material-induced skinirritation of a subject in need thereof, comprising the steps of: (a)adding an α-oxocarboxylic acid to the perfumery raw material having afirst POV level; and (b) mixing the α-oxocarboxylic acid into theperfumery raw material for a time sufficient to reduce the first POVlevel to a pre-determined second lower level, wherein the pre-determinedsecond lower level is sufficient to reduce, prevent, or ameliorate theperfumery raw material-induced skin irritation of the subject.

An alternate aspect presented herein, provides a method for reducing thePOV of a formulated perfume, comprising the steps of: adding anα-oxocarboxylic acid to the formulated perfume having a first POV level;and mixing the α-oxocarboxylic acid into the formulated perfume for atime sufficient to reduce the first POV level to a pre-determined secondlower level.

An alternate aspect presented herein, provides a method for reducing,preventing, or ameliorating formulated perfume-induced skin irritationof a subject in need thereof, comprising the steps of: (a) adding anα-oxocarboxylic acid to the formulated perfume having a first POV level;and (b) mixing the α-oxocarboxylic acid into the formulated perfume fora time sufficient to reduce the first POV level to a pre-determinedsecond lower level, wherein the pre-determined second lower level issufficient to reduce, prevent, or ameliorate the formulatedperfume-induced skin irritation of the subject.

An alternate aspect presented herein, provides a method for reducing thePOV of a formulated personal care product, comprising the steps of:adding an α-oxocarboxylic acid to the formulated personal care producthaving a first POV level; and mixing the α-oxocarboxylic acid into theformulated personal care product for a time sufficient to reduce thefirst POV level to a pre-determined second lower level.

An alternate aspect presented herein, provides a method for reducing,preventing, or ameliorating formulated personal care product-inducedskin irritation of a subject in need thereof, comprising the steps of:(a) adding an α-oxocarboxylic acid to the formulated personal careproduct having a first POV level; and (b) mixing the α-oxocarboxylicacid into the formulated personal care product for a time sufficient toreduce the first POV level to a pre-determined second lower level,wherein the pre-determined second lower level is sufficient to reduce,prevent, or ameliorate the formulated personal care product-induced skinirritation of the subject.

An alternate aspect presented herein, provides a method for reducing thePOV of a formulated cosmetic product, comprising the steps of: adding anα-oxocarboxylic acid to the formulated cosmetic product having a firstPOV level; and mixing the α-oxocarboxylic acid into the formulatedcosmetic product for a time sufficient to reduce the first POV level toa pre-determined second lower level.

An alternate aspect presented herein, provides a method for reducing,preventing, or ameliorating formulated cosmetic product-induced skinirritation of a subject in need thereof, comprising the steps of: (a)adding an α-oxocarboxylic acid to the formulated cosmetic product havinga first POV level; and (b) mixing the α-oxocarboxylic acid into theformulated cosmetic product for a time sufficient to reduce the firstPOV level to a pre-determined second lower level, wherein thepre-determined second lower level is sufficient to reduce, prevent, orameliorate the formulated cosmetic product-induced skin irritation ofthe subject.

An alternate aspect presented herein, provides a method for reducing thePOV of a formulated homecare product, comprising the steps of: adding anα-oxocarboxylic acid to the formulated homecare product having a firstPOV level; and mixing the α-oxocarboxylic acid into the formulatedhomecare product for a time sufficient to reduce the first POV level toa pre-determined second lower level.

An alternate aspect presented herein, provides a method for reducing,preventing, or ameliorating formulated homecare product-induced skinirritation of a subject in need thereof, comprising the steps of: (a)adding an α-oxocarboxylic acid to the formulated homecare product havinga first POV level; and (b) mixing the α-oxocarboxylic acid into theformulated homecare product for a time sufficient to reduce the firstPOV level to a pre-determined second lower level, wherein thepre-determined second lower level is sufficient to reduce, prevent, orameliorate the formulated homecare product-induced skin irritation ofthe subject.

In one aspect, the method is performed at room temperature. In oneaspect, the method is performed at a temperature ranging from −20degrees Celsius to 78 degrees Celsius.

In one aspect the perfumery raw material is selected from the groupconsisting of a synthetic ingredient, a natural product, an essentialoil, and a natural extract.

In one aspect, the perfumery raw material is citrus oil.

In one aspect, the perfumery raw material is treated prior to theincorporation into a perfume.

In one aspect, the perfumery raw material is treated after theincorporation into a perfume.

In one aspect, the pre-determined second lower level is between 5 and 20mmol/L. In an alternate aspect, the pre-determined second lower level isbetween 5 and 19 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is between 5 and 18 mmol/L. In an alternate aspect,the pre-determined second lower level is between 5 and 17 mmol/L. In analternate aspect, the pre-determined second lower level is between 5 and16 mmol/L. In an alternate aspect, the pre-determined second lower levelis between 5 and 15 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is between 5 and 14 mmol/L. In an alternate aspect,the pre-determined second lower level is between 5 and 13 mmol/L. In analternate aspect, the pre-determined second lower level is between 5 and12 mmol/L. In an alternate aspect, the pre-determined second lower levelis between 5 and 11 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is between 5 and 10 mmol/L. In an alternate aspect,the pre-determined second lower level is between 5 and 9 mmol/L. In analternate aspect, the pre-determined second lower level is between 5 and8 mmol/L. In an alternate aspect, the pre-determined second lower levelis between 5 and 7 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is between 5 and 6 mmol/L.

In one aspect, the pre-determined second lower level is between 6 and 20mmol/L. In an alternate aspect, the pre-determined second lower level isbetween 7 and 20 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is between 8 and 20 mmol/L. In an alternate aspect,the pre-determined second lower level is between 9 and 20 mmol/L. In analternate aspect, the pre-determined second lower level is between 10and 20 mmol/L. In an alternate aspect, the pre-determined second lowerlevel is between 11 and 20 mmol/L. In an alternate aspect, thepre-determined second lower level is between 12 and 20 mmol/L. In analternate aspect, the pre-determined second lower level is between 13and 20 mmol/L. In an alternate aspect, the pre-determined second lowerlevel is between 14 and 20 mmol/L. In an alternate aspect, thepre-determined second lower level is between 15 and 20 mmol/L. In analternate aspect, the pre-determined second lower level is between 16and 20 mmol/L. In an alternate aspect, the pre-determined second lowerlevel is between 17 and 20 mmol/L. In an alternate aspect, thepre-determined second lower level is between 18 and 20 mmol/L. In analternate aspect, the pre-determined second lower level is between 19and 20 mmol/L.

In one aspect, the pre-determined second lower level is 20 mmol/L. In analternate aspect, the pre-determined second lower level is 19 mmol/L. Inan alternate aspect, the pre-determined second lower level is 18 mmol/L.In an alternate aspect, the pre-determined second lower level is 17mmol/L. In an alternate aspect, the pre-determined second lower level is16 mmol/L. In an alternate aspect, the pre-determined second lower levelis 15 mmol/L. In an alternate aspect, the pre-determined second lowerlevel is 14 mmol/L. In an alternate aspect, the pre-determined secondlower level is 13 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is 12 mmol/L. In an alternate aspect, thepre-determined second lower level is 11 mmol/L. In an alternate aspect,the pre-determined second lower level is 10 mmol/L. In an alternateaspect, the pre-determined second lower level is 9 mmol/L. In analternate aspect, the pre-determined second lower level is 8 mmol/L. Inan alternate aspect, the pre-determined second lower level is 7 mmol/L.In an alternate aspect, the pre-determined second lower level is 6mmol/L. In an alternate aspect, the pre-determined second lower level is5 mmol/L. In an alternate aspect, the pre-determined second lower levelis 4 mmol/L. In an alternate aspect, the pre-determined second lowerlevel is 3 mmol/L. In an alternate aspect, the pre-determined secondlower level is 2 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is 1 mmol/L. In an alternate aspect, thepre-determined second lower level is less than 1 mmol/L.

In one aspect, the pre-determined second lower level is a 10% reductionin the POV. In an alternate aspect, the pre-determined second lowerlevel is a 20, or 30, or 40, or 50, or 60, or 70, or 80, or 90, or 100%reduction in the POV.

An alternate aspect presented herein, provides a method for reducing thePOV of a food raw material, comprising the steps of: adding anα-oxocarboxylic acid to the food raw material having a first POV level;and mixing the α-oxocarboxylic acid into the food raw material for atime sufficient to reduce the first POV level to a pre-determined secondlower level.

An alternate aspect presented herein, provides a method for reducing thePOV of a flavored article, comprising the steps of: adding anα-oxocarboxylic acid to the flavored article having a first POV level;and mixing the α-oxocarboxylic acid into the flavored article for a timesufficient to reduce the first POV level to a pre-determined secondlower level.

Without intending to be limited to any particular theory, reducing thePOV of a flavored article or a food raw material, prevents, reduces, orinhibits the formation of the intermediate glyceride hydroperoxides inthe flavored article or the food raw material. Reducing, or inhibiting,or preventing the formation of the intermediate glyceride hydroperoxidesin the flavored article or the food raw material may prevent, reduce, ordelay the development of rancidity in the flavored article or the foodraw material.

A flavored article includes, for example, a food product (e.g., abeverage), a sweetener such as a natural sweetener or an artificialsweetener, a pharmaceutical composition, a dietary supplement, anutraceutical, a dental hygienic composition and a cosmetic product. Theflavored article may further contain at least one flavoring.

In some aspects, the at least one flavoring may further modify the tasteprofile or taste attributes of the flavored article.

In some aspects, the flavored article is a food product including, forexample, but not limited to, fruits, vegetables, juices, meat productssuch as ham, bacon and sausage, egg products, fruit concentrates,gelatins and gelatin-like products such as jams, jellies, preserves andthe like, milk products such as ice cream, sour cream and sherbet,icings, syrups including molasses, corn, wheat, rye, soybean, oat, riceand barley products, nut meats and nut products, cakes, cookies,confectioneries such as candies, gums, fruit flavored drops, andchocolates, chewing gums, mints, creams, pies and breads.

In some aspects, the food product is a beverage including, for example,but not limited to, juices, juice containing beverages, coffee, tea,carbonated soft drinks, such as COKE and PEPSI, non-carbonated softdrinks and other fruit drinks, sports drinks such as GATORADE andalcoholic beverages such as beers, wines and liquors.

A flavored article may also include prepared packaged products, such asgranulated flavor mixes, which upon reconstitution with water providenon-carbonated drinks, instant pudding mixes, instant coffee and tea,coffee whiteners, malted milk mixes, pet foods, livestock feed, tobacco,and materials for baking applications, such as powdered baking mixes forthe preparation of breads, cookies, cakes, pancakes, donuts and thelike.

A flavored article may also include diet or low-calorie food andbeverages containing little or no sucrose. Flavored articles may alsoinclude condiments such as herbs, spices and seasonings, flavorenhancers (e.g., monosodium glutamate), dietetic sweeteners and liquidsweeteners.

In some aspects, the flavored article is a pharmaceutical composition, adietary supplement, a nutraceutical, a dental hygienic composition or acosmetic product.

Dental hygiene compositions are known in the art and include, forexample, but not limited to, a toothpaste, a mouthwash, a plaque rinse,a dental floss, a dental pain reliever (such as ANBESOL) and the like.In some aspects, the dental hygiene composition includes one naturalsweetener. In some aspects, the dental hygiene composition includes morethan one natural sweetener. In some aspects, the dental hygienecomposition includes sucrose and corn syrup, or sucrose and aspartame.

In some aspects, a cosmetic product includes, for example, but notlimited to, a face cream, a lipstick, a lip gloss and the like. Othersuitable cosmetic products of use in this disclosure include a lip balm,such as CHAPSTICK or BURT'S BEESWAX Lip Balm.

An alternate aspect presented herein, provides a method for increasingthe shelf life of a food raw material, comprising the steps of: addingan α-oxocarboxylic acid to the food raw material having a first POVlevel; and mixing the α-oxocarboxylic acid into the food raw materialfor a time sufficient to reduce the first POV level to a pre-determinedsecond lower level. Without intending to be limited to any particulartheory, the reduction of the first POV level to a pre-determined secondlower level prevents, reduces, or inhibits the formation of theintermediate glyceride hydroperoxides in the food raw material,resulting in the prevention, reduction, inhibition of the development ofrancidity in the food raw material.

Without intending to be limited to any particular theory, the food rawmaterial may be employed as a solvent for a flavoring ingredient, or,alternatively, the food raw material itself may be a flavoringingredient.

An alternate aspect presented herein, provides a method for increasingthe shelf life of flavored article, comprising the steps of: adding anα-oxocarboxylic acid to the flavored article having a first POV level;and mixing the α-oxocarboxylic acid into the flavored article for a timesufficient to reduce the first POV level to a pre-determined secondlower level. Without intending to be limited to any particular theory,the reduction of the first POV level to a pre-determined second lowerlevel prevents, reduces, or inhibits the formation of the intermediateglyceride hydroperoxides in the flavored article, resulting in theprevention, reduction, inhibition of the development of rancidity in theflavored article.

In one aspect, the food raw material is selected from the groupconsisting of a fat, an oil, or a derivative thereof. In one aspect, thederivative thereof is selected from the group consisting of amonoglyceride, a diglyceride, and a phospholipid. In one aspect, thephospholipid is selected from the group consisting of a lecithin, aphosphatidyl ethanolamine, and a modified triglyceride.

In one aspect, the food raw material is treated prior to theincorporation into a flavored article. In an alternate aspect the foodraw material is incorporated after the incorporation into a flavoredarticle.

In one aspect, the food raw material is a cooking oil. Examples ofcooking oils suitable for treatment according to the aspects describedherein include, but are not limited to: olive oil, palm oil, soybeanoil, canola oil (rapeseed oil), corn oil, peanut oil, other vegetableoils, and animal-based oils, such as, for example, butter or lard.

In one aspect, the method is performed at room temperature. In oneaspect, the method is performed at a temperature ranging from −20degrees Celsius to 78 degrees Celsius.

In one aspect, the pre-determined second lower level is between 0 and 6mmol/L. In an alternate aspect, the pre-determined second lower level isbetween 0 and 5 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is between 0 and 4 mmol/L. In an alternate aspect,the pre-determined second lower level is between 0 and 3 mmol/L. In analternate aspect, the pre-determined second lower level is between 0 and2 mmol/L. In an alternate aspect, the pre-determined second lower levelis between 0 and 1 mmol/L.

In one aspect, the pre-determined second lower level is between 1 and 6mmol/L. In an alternate aspect, the pre-determined second lower level isbetween 2 and 5 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is between 3 and 5 mmol/L. In an alternate aspect,the pre-determined second lower level is between 4 and 5 mmol/L.

In one aspect, the pre-determined second lower level is 5 mmol/L. In analternate aspect, the pre-determined second lower level is 4 mmol/L. Inan alternate aspect, the pre-determined second lower level is 3 mmol/L.In an alternate aspect, the pre-determined second lower level is 2mmol/L. In an alternate aspect, the pre-determined second lower level is1 mmol/L. In an alternate aspect, the pre-determined second lower levelis 0.9 mmol/L. In an alternate aspect, the pre-determined second lowerlevel is 0.8 mmol/L. In an alternate aspect, the pre-determined secondlower level is 0.7 mmol/L. In an alternate aspect, the pre-determinedsecond lower level is 0.6 mmol/L. In an alternate aspect, thepre-determined second lower level is 0.5 mmol/L. In an alternate aspect,the pre-determined second lower level is 0.4 mmol/L. In an alternateaspect, the pre-determined second lower level is 0.3 mmol/L. In analternate aspect, the pre-determined second lower level is 0.2 mmol/L.In an alternate aspect, the pre-determined second lower level is 0.1mmol/L. In an alternate aspect, the pre-determined second lower level is0 mmol/L.

In one aspect, the pre-determined second lower level is a 10% reductionin the POV. In an alternate aspect, the pre-determined second lowerlevel is a 20, or 30, or 40, or 50, or 60, or 70, or 80, or 90, or 100%reduction in the POV.

In one aspect, the α-oxocarboxylic acid has FEMA-GRAS status. In oneaspect, the α-oxocarboxylic acid is selected from the group consistingof: pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyricacid, 2-oxo-2-furanacetic acid, oxaloacetic acid, α-ketoglutaric acid,2-oxopentandioate, indole-3-pyruvic acid, 2-thiopheneglyoxylic acid,trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid,phenylpyruvic acid, 2-oxooctanoic acid, and mixtures thereof.

In some aspects, the at least one α-oxocarboxylic acid is added to theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialas a salt. The salt may be formed by reacting the at least oneα-oxocarboxylic acid with an organic base.

In the aspects where the at least one α-oxocarboxylic acid is amono-acid, the resultant salt may be a mono-salt. In the aspects wherethe at least one α-oxocarboxylic acid is a di-acid, the resultant saltmay be a mono-salt, or a di-salt.

Examples of suitable organic bases include, but are not limited to theorganic bases described in Examples 7-11 below, polymeric amines,polyetylamines, and the like.

Alternatively, the salt may be formed by reacting the at least oneα-oxocarboxylic acid with a cation selected from the group consistingof: Na⁺, K⁺, Mg²⁺, and Ca²⁺.

An example of an ammonium salt includes the ammonium salt formed byreacting the at least one α-oxocarboxylic acid with N-methyldiethanolamine.

In some aspects, the molar ratio of the at least one α-oxocarboxylicacid to N-methyl diethanolamine may be 1:2, or 1:1, or 2:1.

In some aspects, the ammonium salt of the at least one α-oxocarboxylicacid possesses surfactant properties. Without intending to be limited toany particular theory, surfactant properties typically arise inmolecules that contain an ionic and/or highly polar functional groups inthe molecule, along with one or more spatially separated, longhydrophobic section(s). If a hydrophobic moiety, such as an alkyl groupwith a sufficient number of carbons (for example, C-8 to C-24) is boundto the ammonium salt of the at least one α-oxocarboxylic acid, theresulting molecule may demonstrate surfactant properties.

Without intending to be limited to any particular theory, an ammoniumsalt of the at least one α-oxocarboxylic acid possessing surfactantproperties, or that is ionic and highly polar may be useful in a varietyof home care and body care consumer products that come in contact withthe user's skin during use.

Examples of ammonium salts of the at least one α-oxocarboxylic acidhaving surfactant properties include, but are not limited to: thediammonium salt made from alpha-ketoglutaric acid and N,N-dimethyldodecylamine in a 1:2 molar ratio, and the monoammonium saltmade from alpha-ketoglutaric acid and N, N-dimethyldodecylamine in a 1:1molar ratio.

In some aspects, the ammonium salt of the at least one α-oxocarboxylicacid possesses emollient properties. Without intending to be limited toany particular theory, emollient properties typically arise in moleculesthat are predominately hydrophobic and inert with low melting points(relative to body temperature) can act as emollients. Useful emollientshave oily or grease-like physical properties, and act as softeningagents and/or moisture barriers when applied to the skin. While theammonium salt of the at least one α-oxocarboxylic acid listed above areionic and highly polar in character, if a sufficient quantity ofhydrophobic moieties can be incorporated into an ammonium salt of the atleast one α-oxocarboxylic acid, the resulting molecule may displayemollient characteristics.

One approach is to use an amine that has three long, hydrophobic or oilysubstituents as the base component of the ammonium salt of the at leastone α-oxocarboxylic acid. Such a molecule may have hydroperoxideconsuming/POV lowering qualities along with emollient properties, andtherefore provide additional benefits to the user. These would be usefulin a variety of body care consumer products that are placed onto theskin during use and left on for extended periods for purposes ofmoisturizing, protecting, or softening the user's skin.

Examples of ammonium salts of the at least one α-oxocarboxylic acidhaving emollient properties include, but are not limited to: thediammonium salt made from alpha-ketoglutaric acid and Tris[2 (2(methoxyethoxy)ethyl]amine in a 1:2 molar ratio.

In some aspects, the at least one α-oxocarboxylic acid may be reactedwith N-methyl diethanolamine by dissolving the at least oneα-oxocarboxylic acid in a solvent, such as, for example, acetone, andadding N-methyl diethanolamine to the solution. The resultant opaque,white emulsion may then be vortexed, during which time a second phasemay coalesce. The mixture may then be placed in a freezer for at least30 minutes, causing the bottom phase to thicken to a waxy solid. Whilestill cold, the top layer may then be easily removed via decantation anddiscarded. Residual acetone may be removed from the bottom product layervia a stream of nitrogen followed by treatment in a vacuum oven at roomtemperature, thereby resulting in a faint yellow, highly viscous oil atroom temperature comprising the diammonium salt.

Other compounds suitable to form an ammonium salt via reaction with theat least one α-oxocarboxylic acid include, 2-(dimethylamino)ethanol, andN, N-dimethyldodecylamine.

In one aspect the salt is an ammonium salt formed by reacting theα-oxocarboxylic acid with a compound selected from the group consistingof: 2-(dimethylamino)ethanol, N, N-dimethyldodecylamine, Tris[2 (2(methoxyethoxy)ethyl]amine, and N-methyl diethanolamine.

Without intending to be limited to any particular theory, the ammoniumsalt of the at least one α-oxocarboxylic acid may prevent acid-catalyzedchemical reactions from occurring that can harm and/or degrade thetreated formulated perfume, body care product, cosmetic product,homecare product, perfumery raw material, flavored article, or food rawmaterial. Alternatively, the ammonium salt of the at least oneα-oxocarboxylic acid may improve the solubility of the at least oneα-oxocarboxylic acid. Alternatively, the ammonium salt of the at leastone α-oxocarboxylic acid may provide an emulsifying effect.

Without intending to be limited to any particular theory, a salt of theat least one α-oxocarboxylic acid, when added to an aqueous systemcomprising the formulated perfume, body care product, cosmetic product,homecare product, perfumery raw material, flavored article, or food rawmaterial may be an emulsifier. Such a composition may be useful forsalad dressings, marinades, sauces, and the like.

In one aspect, the ammonium salt of the at least one α-oxocarboxylicacid may be further combined with at least one other agent. In oneaspect, the at least one other agent is chitosan.

In one aspect, alpha-ketoglutaric acid is added to a mixture of palmiticacid and chitosan. Such a composition may be an emulsifier for the foodoil in an aqueous system, and may be useful for salad dressings,marinades, sauces, and the like.

In one aspect, the time sufficient to reduce the POV to a pre-determinedsecond lower level is 30, or 29, or 28, or 27, or 26, or 25, or 24, or23, or 22, or 21, or 20, or 19, or 18, or 17, or 16, or 15, or 14, or13, or 12, or 11, or 10, or 9, or 8, or 7, or 6, or 5, or 4, or 3, or 2,or 1 day(s).

In one aspect, the time sufficient to reduce the POV to a pre-determinedsecond lower level is greater than 24 hours. In one aspect, the timesufficient to reduce the POV to a pre-determined second lower level is48, or 47, or 46, or 45, or 44, or 43, or 42, or 41, or 40, or 39, or38, or 37, or 36, or 35, or 34, or 33, or 32, or 31, or 30, or 29, or28, or 27, or 26, or 25, or 24, or 23, or 22, or 21, or 20, or 19, or18, or 17, or 16, or 15, or 14, or 13, or 12, or 11, or 10, or 9, or 8,or 7, or 6, or 5, or 4, or 3, or 2, or 1 hour(s).

In one aspect, the time sufficient to reduce the POV to a pre-determinedsecond lower level is 60 minutes or less. In one aspect, the timesufficient to reduce the POV to a pre-determined second lower level is60, or 50, or 40, or 30, or 20, or 10, or 9, or 8, or 7, or 6, or 5, or4, or 3, or 2, or 1 minute.

Without intending to be limited to any particular theory, the amount ofthe α-oxocarboxylic acid and/or the rate at which the α-oxocarboxylic isadded to the formulated perfume, body care product, cosmetic product,homecare product, perfumery raw material, flavored article, or food rawmaterial is controlled to ensure that an excess of the α-oxocarboxylicdoes not accumulate. An excess accumulation of the α-oxocarboxylic mayresult, for example, in acid-catalyzed damage to the formulated perfume,body care product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material.

The amount of the α-oxocarboxylic acid that is added to the formulatedperfume, body care product, perfumery raw material, flavored article, orfood raw material is dependent on several factors, including, but notlimited to, the stability of the α-oxocarboxylic acid in solution, thesolubility of the α-oxocarboxylic acid in the formulated perfume, bodycare product, perfumery raw material, flavored article, or food rawmaterial, the pKa of the α-oxocarboxylic acid, the rate of reduction ofthe POV, the effect the α-oxocarboxylic acid has on the olfactiveproperties and/or taste of the formulated perfume, body care product,perfumery raw material, flavored article, or food raw material.

By way of illustration, pyruvic acid, phenylpyruvic acid, and2-oxovaleric acid possess strong aromas are used as FEMA-GRAS flavoringcomponents. In these aspects, the intrinsic odors of the α-oxocarboxylicacid may alter, or be incompatible with the organoleptic quality of aformulated perfume, for example.

An alternative to using an odorless α-oxocarboxylic acid in the aspectsdescribed herein is the use of an α-oxocarboxylic acid that iscompatible with the fragrance of the perfume, and when consumed byreaction with hydroperoxides, that also liberates a carboxylic acid thatis compatible with the fragrance. By way of illustration,indole-3-pyruvic acid nay be used to reduce the POV of a fragrance thathas an indolic character (i.e. contains perceivable amounts of indoleand/or skatole).

Examples of an α-oxocarboxylic acid that is odorless includeα-ketoglutaric acid. Without intending to be limited to any particulartheory, an odorless α-oxocarboxylic acid may reduce the POV of aformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialwith a lower impact on the organoleptic properties of the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material, comparedto an α-oxocarboxylic acid that has an odor.

The solubility of the α-oxocarboxylic acid may change if the compositioncomprising the α-oxocarboxylic acid is formulated differently. Usingα-ketoglutaric acid as an example, the solubility of the α-oxocarboxylicacid may be low in a perfume raw material such citrus oil. However, thesolubility of the α-oxocarboxylic acid may increase, if the perfume rawmaterial is added to a hydroalcoholic perfume base (a solutioncomprising from 80% to 90% ethanol in water). In these aspects, if theα-oxocarboxylic acid is a strong acid, the amount of the α-oxocarboxylicacid in solution in the hydroalcoholic perfume base may have to belimited, to prevent alterations of the organoleptic properties on theperfume raw materials or the formulated perfume due to theacid-catalyzed degradation of the perfume raw material.

Examples of aspects where the α-oxocarboxylic acid may be unstable insolution include oxaloacetic acid, which is unstable in aqueoussolution. In these aspects, the oxaloacetic acid breaks down to pyruvicacid, and carbon dioxide. In these aspects, reduction of the POV of theformulated perfume, body care product, perfumery raw material, flavoredarticle, or food raw material may be via the oxaloacetic acid, thepyruvic acid, or any combination thereof.

In some aspects, the solubility of the α-oxocarboxylic acid in theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialis low. By way of illustration, at the lower limit of solubility, theα-oxocarboxylic acid may be practically insoluble in the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material. Incontrast, at the upper limit of solubility, the α-oxocarboxylic acid maybe fully miscible in the formulated perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material.

Examples of aspects where the solubility of the α-oxocarboxylic acid informulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialis low include, but are not limited to pyruvic acid in citrus oil. Inthese aspects, the α-oxocarboxylic acid may be added at a concentrationin excess of the solubility, thus forming a two-phase system, whereinone phase consists of the α-oxocarboxylic acid. Without intending to belimited to any particular theory, components of the formulated perfume,body care product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material may partition into thephase consisting of the α-oxocarboxylic acid. Exposure of the componentsof the formulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialto the phase consisting of the α-oxocarboxylic acid may result inchemical changes/damage to acid-sensitive compounds in the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material.

By way of illustration, essential oils are composed largely of terpenecompounds. As a class, terpenes are generally subject to acid-catalyzedrearrangements. Consequently, exposure of the components of theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialto the phase consisting of the α-oxocarboxylic acid may result inchemical changes/damage to acid-sensitive compounds in the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material, andconsequently alter the organoleptic properties of the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material.

Consequently, in some aspects presented herein, the α-oxocarboxylic acidis added at a rate that minimizes, or prevents the formation of thesecond phase consisting of the α-oxocarboxylic acid. Such rate ofaddition may be equal to the rate of the chemical reaction that reducesthe POV of the formulated perfume, body care product, cosmetic product,homecare product, perfumery raw material, flavored article, or food rawmaterial. Without intending to be limited to any particular theory,addition of the α-oxocarboxylic acid at the same rate as the chemicalreaction may prevent the α-oxocarboxylic acid from accumulating andthereby keep the second phase volume minimized, which will reducepartitioning of the formulated perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material into the highly acidic phase consisting of theα-oxocarboxylic acid.

Alternatively, effective dispersion of the α-oxocarboxylic acid in tothe formulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialmay increase the rate of the chemical reaction that reduces the POV ofthe formulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material,by increasing the surface area of contact between the two phases of thetwo phase system.

Examples of aspects where the solubility of the α-oxocarboxylic acid inthe formulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialis not low include, but are not limited to 2-oxo-valeric acid. Withoutintending to be limited to any particular theory, in aspects where thesolubility of the α-oxocarboxylic acid in the formulated perfume, bodycare product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material is not low may resultin the formation of a single phase. Here, the added α-oxocarboxylic acidis soluble in the formulated perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material being treated, and therefore will be dilutedimmediately upon addition. In this case, if the rate of addition isclose to the rate of reaction, the α-oxocarboxylic acid will also beconsumed as it is being added. The concentration of the α-oxocarboxylicacid will remain low, and acid-induced changes will be minimized.

In an alternate aspect, the concentration of un-reacted α-oxocarboxylicacid is minimized by using a buffer, wherein the α-oxocarboxylic acid ispresent as a deprotonated anion.

The anionic form of an α-oxocarboxylic acid will likely be unreactivetoward a hydroperoxide relative to the protonated, acidic form. However,as the acidic form is consumed by reaction with hydroperoxides, theequilibrium of the α-oxocarboxylic acid-base pair will quicklyreestablish itself in accordance with the pKa of α-oxocarboxylic acid;the anionic form will instantly capture a proton from the media toproduce more of the hydroperoxide-reactive acidic form of theα-oxocarboxylic acid. In this way, the bulk acidity of the media can bemaintained at a mild pH level, one that will not cause acid damage tothe components of the formulated perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material. But simultaneously, there will be a relatively lowbut fixed level of the α-oxocarboxylic acid in the reactive protonatedform, replenished as soon as it is consumed from a sink of therelatively inert anionic form.

For example, using pyruvic acid for illustrative purposes only, pyruvicacid has a pKa of 2.50, buffering the formulated perfume, body careproduct, cosmetic product, homecare product, perfumery raw material,flavored article, or food raw material to pH 5.5 (a difference of 3 logunits), would result in 10³ (or 1000) times the concentration ofpyruvate anion, compared to pyruvic acid (as per theHenderson-Hasselbalch equation).

In one aspect, the concentration of the α-oxocarboxylic acid ranges from0.001 to 10 weight percent, after addition to the formulated perfume,body care product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material. In one aspect theconcentration of the α-oxocarboxylic acid is 10 weight percent, afteraddition to the formulated perfume, body care product, cosmetic product,homecare product, perfumery raw material, flavored article, or food rawmaterial. Alternatively, the concentration of the α-oxocarboxylic acidis 9, or 8, or 7, or 6, or 5, or 4, or 3, or 2, or 1, or 0.9, or 0.8, or0.7, or 0.6, or 0.5, or 0.4, or 0.3, or 0.2, or 0.1, or 0.09, or 0.08,or 0.07, or 0.06, or 0.05, or 0.04, or 0.03, or 0.02, or 0.01, or 0.009,or 0.008, or 0.007, or 0.006, or 0.005, or 0.004, or 0.003, or 0.002, or0.001 weight percent, after addition to the formulated perfume, bodycare product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material.

The α-oxocarboxylic acid can be added directly to the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material, or,alternatively, the α-oxocarboxylic acid can be diluted prior to additionto the formulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material.Any diluent that may be used in perfumery may be used. Suitable diluentsinclude, but are not limited to isopropanol, ethanol, diglyme,triethyleneglycol, and the like. The α-oxocarboxylic acid may be diluted1:1, or 1:2, or 1:3, or 1:4, or more with the diluent.

Without intending to be limited by any particular theory, the choice ofdiluent may also influence the amount of the α-oxocarboxylic acid thatmay be added to the formulated perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material. In addition, the choice of diluent may also influencethe rate at which the α-oxocarboxylic acid that is be added to theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material.For example, by way of illustration, using pyruvic acid as theα-oxocarboxylic acid, and ethanol as the solvent, the pyruvic acid mustbe added in an amount, and/or a at a rate that minimizes the formationof an ester with the ethanol.

The α-oxocarboxylic acid can be added to any volume of the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material. Forexample, the α-oxocarboxylic acid can be added can be added to 1000 mlof formulated perfume, body care product, or perfumery raw material, or900, or 800, or 700, or 600, or 500, or 400, or 300, or 200, or 100, or90, or 80, or 70, or 60, or 50, or 40, or 30, or 20, or 10, or 9, or 8,or 7, or 6, or 5, or 4, or 3, or 2, or 1 ml of formulated perfume, bodycare product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material.

In one aspect, the α-oxocarboxylic acid may be added to the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material over 80minutes. Alternatively, the α-oxocarboxylic acid may be added to theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialover 70, or 60, or 50, or 40, or 30, or 20, or 10, or 9, or 8, or 7, or6, or 5, or 4, or 3, or 2, or 1 minute(s).

In one aspect, the α-oxocarboxylic acid is added to the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material at a rateof 0.25 ml per minute. In some aspects, the rate of addition is greaterthan 0.25 ml per minute. In some aspects, the rate of addition is lessthan 0.25 ml per minute.

In some aspects, the rate at which the α-oxocarboxylic acid is added tothe formulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialis constant. In some aspects, the rate at which the α-oxocarboxylic acidis added to the formulated perfume, body care product, cosmetic product,homecare product, perfumery raw material, flavored article, or food rawmaterial varies. In one aspect, the α-oxocarboxylic acid is added to theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialat a rate equal to the rate at which the α-oxocarboxylic acid isoxidized. In some aspects, the rate at which the α-oxocarboxylic acid isoxidized may be determined by measuring the POV in the treatedformulated perfume, body care product, or perfumery raw material.Referring to FIGS. 2 to 4, by way of illustration, the rate of reductionof POV may have a first rate, which is greater than a second rate. Inthe aspect illustrated, the duration of the first rate is less than theduration of the second rate.

In an alternate aspect, the α-oxocarboxylic acid may be added, andsubsequently quenched after a period of time. The α-oxocarboxylic acidmay be quenched 80 minutes after addition to the substance.Alternatively, the α-oxocarboxylic acid may be quenched 70, or 60, or50, or 40, or 30, or 20, or 10, or 9, or 8, or 7, or 6, or 5, or 4, or3, or 2, or 1 minute(s) after addition to the substance.

In one aspect, the method further comprises removing the excessα-oxocarboxylic acid from the formulated perfume, body care product,cosmetic product, homecare product, perfumery raw material, flavoredarticle, or food raw material having a POV of a pre-determined secondlower level.

In one aspect, the excess α-oxocarboxylic acid is removed from theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialvia a liquid-liquid extraction.

In one aspect, the excess α-oxocarboxylic acid is removed from theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialvia a liquid-liquid extraction using water.

In one aspect, other byproducts of the reaction that reduces the POV ofthe formulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialto the pre-determined second lower level are also removed by theliquid-liquid extraction. All byproducts, or, alternatively, a portionof the byproducts may be removed.

In one aspect, the method further comprises treating the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material afterremoving the excess α-oxocarboxylic acid to reduce the acidity of thesubstance. In some aspects, the treatment comprises the addition of abuffer, such as, for example, triethanolamine, orN-methyldiethanolamine, and the like.

In one aspect, the substance is treated with a carbonate salt to reducethe acidity of the formulated perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material.

In one aspect, the method for reducing the POV of formulated perfume,body care product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material comprises the steps of:

-   -   a) introducing the formulated perfume, body care product,        cosmetic product, homecare product, perfumery raw material,        flavored article, or food raw material into a reaction vessel,        wherein the formulated perfume, body care product, cosmetic        product, homecare product, perfumery raw material, flavored        article, or food raw material is under an inert gas, such as,        for example, argon;    -   b) introducing the α-oxocarboxylic acid to the formulated        perfume, body care product, cosmetic product, homecare product,        perfumery raw material, flavored article, or food raw material        at a rate of 0.25 ml per minute, wherein the α-oxocarboxylic        acid is diluted 1:4 with a diluent, wherein the α-oxocarboxylic        acid to the formulated perfume, body care product, cosmetic        product, homecare product, perfumery raw material, flavored        article, or food raw material is constantly stirred during the        introduction;    -   c) introducing water and anhydrous sodium carbonate to the        mixture and allowing the reaction to continue until there is no        longer any visible evolution of CO₂; and    -   d) discarding the aqueous layer, thereby obtaining a formulated        perfume, body care product, cosmetic product, homecare product,        perfumery raw material, flavored article, or food raw material        with a POV having a pre-determined second lower level.

Examples of a method according to the aspect described above can befound in Examples 1 to 4 below.

In some aspects, the second phase of the α-oxocarboxylic acid in theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialis a “leave-in” composition of the α-oxocarboxylic acid. Withoutintending to be limited to any particular theory, the amountα-oxocarboxylic acid present in the two phases is in equilibrium, andthe reduction of POV may result in the α-oxocarboxylic acid moving fromthe phase consisting of α-oxocarboxylic acid, into the phase containingthe formulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material.One example of this aspect is described in Example 5 below.

In some aspects, the “leave-in” composition of the α-oxocarboxylic acidcomprises a single phase composition with the formulated perfume, bodycare product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material. In these aspects, thecomposition further comprises a buffer, wherein the pH is configured tomaintain the majority of the α-oxocarboxylic acid present in anon-protonated form, wherein the non-protonated form is incapable ofreacting with the chemical species that contribute to the POV of thecomposition (including peroxides, organic hydroperoxides,peroxyhemiacetals). Without intending to be limited to any particulartheory, the amount of the α-oxocarboxylic acid present in non-protonatedform is in equilibrium with an amount of amount of the α-oxocarboxylicacid present in protonated form, and the reduction of POV may result inthe α-oxocarboxylic acid moving from the non-protonated from to theprotonated form. One example of this aspect is described in Example 4below.

In these instances, the “leave-in” compositions of the α-oxocarboxylicacid is capable of reducing POV for a prolonged period of time.

Accordingly, one aspect presented herein, provides a compositioncomprising: (a) a formulated perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material, and (b) an α-oxocarboxylic acid, wherein theα-oxocarboxylic acid is present in the composition in an amountsufficient to decrease the POV from a first level to a pre-determinedsecond lower level.

In one aspect, the α-oxocarboxylic acid is present in the composition inan amount sufficient to prevent the pre-determined second lower levelfrom changing with time. The time may be hours, days, weeks, or longer.

One aspect presented herein, provides a composition comprising: (a) aformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material,and (b) an α-oxocarboxylic acid, wherein the α-oxocarboxylic acid ispresent in the composition in an amount sufficient to reduce, prevent,or ameliorate an increase in the POV of the formulated perfume, bodycare product, cosmetic product, homecare product, perfumery rawmaterial, flavored article, or food raw material.

In one aspect, the concentration of the α-oxocarboxylic acid in thecomposition ranges from 0.001 to 10 weight percent.

In one aspect, the α-oxocarboxylic acid is selected from the groupconsisting of: pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid,2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid,α-ketoglutaric acid, 2-oxopentandioate, indole-3-pyruvic acid,2-thiopheneglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid,4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid, andmixtures thereof.

In one aspect, the perfumery raw material is citrus oil.

An example of a composition according to the aspect described above canbe found in Example 5 below.

In some aspects, the at least one α-oxocarboxylic acid, or a saltthereof may be applied to, or incorporated into, or covalently bound toa solid substrate, wherein the solid substrate comprising the at leastone α-oxocarboxylic acid, or a salt thereof is used to treat aformulated perfume, body care product, cosmetic product, perfumery rawmaterial, flavored article, or food raw material.

Any inert, finely divided or high surface area material may be used asthe solid support. Examples include, but are not limited to: metals,glass, expanded ceramics, plastics, or inorganic solids. In addition,the solid support may comprise the bottom and/or the walls of a vesselcontaining the formulated perfume, body care product, cosmetic product,perfumery raw material, flavored article, or food raw material.

In some aspects, the solid support has a high surface are: volume ratio.Examples of such solid supports include, but are not limited to steelwool. An example of a composition treated according to the aspectemploying a solid support as described above can be found in Example 24below.

The present invention is best illustrated but is not limited to thefollowing examples.

EXAMPLES Example 1: Reduction of POV in Citrus Oil According to OneAspect Presented Herein Using Pyruvic Acid

50 mL of mixed citrus oils (orange, lemon, lime, mandarin, bergamot, andtangerine) were placed in a 100 round bottom flask at room temperature,along with a stir bar and an argon gas blanket.

A 4:1 v/v isopropanol/pyruvic acid solution was made. 20 mL of thispyruvic acid solution was dripped into the stirred citrus oils at a rateof 0.25 mL/minute via the use of a syringe pump.

When the addition was complete, 10 mL of water and 100 mg of anhydroussodium carbonate was added to the flask, and the stirring wasmaintained. When the visible evolution of CO₂ had stopped (about 2-4minutes), the aqueous layer was removed with a pipette and discarded.POV measurements were made on the mixed citrus oil before and after thepyruvic acid treatment.

POV before treatment was 27.261 mEq/L, and the POV after treatment was4.786 mEq./L. This was about an 82% reduction in POV.

Example 2: Reduction of POV in Limonene According to One AspectPresented Herein Using 2-Oxo-Valeric Acid

10 mL of autoxidized limonene was placed in a 30 mL glass vial at roomtemperature, along with a stir bar and an argon gas blanket. 100 μL of2-oxovaleric acid was added. The vial was shaken once and allowed tostand for 50 minutes. No further treatment was done prior to the POVtesting. POV measurements were made on the limonene before and after the2-oxovaleric acid treatment. POV before treatment was 65.97 mEq./L, andPOV after treatment was 17.21 mEq./L. This was an approximately 74%reduction in POV.

Example 3: Reduction of POV in Limonene According to One AspectPresented Herein Using 2-Oxo-Butyric Acid

20 mL of autoxidized limonene was placed in a 30 mL glass vial at roomtemperature, along with a stir bar and an argon gas blanket. 250 μL of2-oxobutyric acid was added. The vial was shaken once and allowed tostand, while being monitored for POV value as a function of time. Thedata collected is shown in the table below.

Time (in min.) since addition of 2-oxobutryric acid POV (in mEq/L) POVreduction (in %) Untreated 66.245 0.0 3 43.680 34.1 20 22.140 66.6 3522.681 65.8 44 19.968 69.9 66 21.406 67.7 116 19.576 70.4 176 20.96468.4

The results showed an initial rapid reduction in POV, followed bydecline in the rate of POV reduction. This may be due to reagentdepletion, but the loss of POV is not sufficient to fully account on amolar basis for all of the added 2-oxobutyric acid. It may be that somehydroperoxides are destroyed very quickly, and other oxidants aredestroyed much more slowly. When an additional 500 μL of 2-oxobutyricacid was added, and the sample allowed to stand for an additional 24hours, the measured POV was 8.577 mEq./L (87.1% total reduction).

Example 4: Reduction of POV in Limonene According to One AspectPresented Herein Using 2-Phenylglyoxylic Acid

20 mL of autoxidized limonene was placed in a 30 mL glass vial at roomtemperature, along with a stir bar and an argon gas blanket. 200 mg ofphenylglyoxylic acid was added, which dissolved. The vial was shakenonce and allowed to stand, while being monitored for POV value as afunction of time. The data collected is shown in the table below.

Time (in min.) since addition of phenylglyoxylic acid POV (in mEq/L) POVreduction (in %) Untreated 44.795 0.0  40 37.035 17.3 150 34.086 23.9190 29.963 33.1 2880 (48 hrs) 17.265 61.5

Example 5: Reduction of POV in Limonene According to One AspectPresented Herein Using 2-Oxo-2-Furanacetic Acid

20 mL of mixed citrus oil was placed in a 30 mL glass vial at roomtemperature, along with a stir bar and an argon gas blanket. 400 mg ofα-oxo-2-furanacetic acid was added. The vial was shaken once and allowedto stand, while being monitored for POV value as a function of time. Themajority of the added α-oxo-2-furanacetic acid did not dissolve, so thelimited solubility of the acid will likely act as a controlled releasemechanism; as the α-oxo-2-furanacetic acid in solution is consumed byhydroperoxides, more will likely dissolve in accordance will thesolubility constant. In this way, the undissolved solid acts as a sinkto maintain a steady, low concentration of α-oxo-2-furanacetic aciddissolved in the mixed citrus oil.

In this case, because the time between measurements was relatively long(days instead of minutes), there is the possibility that the untreatedmixed citrus oil will oxidize further during the course of theexperiment. Therefore, the POV of the treated oil was still comparedwith the POV of the untreated oil, but the measurement of the untreatedoil was re-determined at each time point (rather than just a single,initial value being used). The data collected is shown in the tablebelow.

Time (in days) since addition of α-Oxo-2- Untreated POV Treated POV POVreduction furanacetic acid (in mEq/L) (in mEq/L) (in %) Untreated 20.59320.593 0.0 2 25.366 18.566 26.8 4 28.581 17.193 39.8 44 29.119 1.10696.2

Example 6: Reduction of POV in a Skin Cream Formulation According to OneAspect Presented Herein Using 2-Oxovaleric Acid or Phenylglyoxylic Acid

A skin cream formulation comprising of 0.5 parts cetylstearyl alcohol,6.0 parts wool wax alcohol, and 93.5 parts white petroleum jelly wascreated as per the German Pharmacopoeia DAB 2008.

The skin cream was divided into two separate preparations. A highlyoxidized limonene sample was added to both preparations, with the firstpreparation receiving a concentration of oxidized limonene approximatelyone third of the concentration of the oxidized limonene in the secondpreparation. Analysis of the oxidized limonene sample showed the sampleto contain a mixture of limonene hydroperoxide isomers.

The initial POV of both the first and second skin cream preparations wastaken, prior to treatment with 2-oxovaleric acid or phenylglyoxylic acidas follows: 2-oxovaleric acid (second preparation), or phenylglyoxylicacid (first preparation) was thoroughly blended into the skin creampreparations. The POV of the preparations were measured, during additionof the 2-oxovaleric acid. After addition of the 2-oxovaleric acid orphenylglyoxylic acid, the treated preparations were allowed to stand atroom temperature. The POV data obtained was corrected for the exactweight of the aliquot of cream titrated at each individual time point,and normalized as a percentage to the starting POV.

The second preparation, containing the highest amount of the oxidizedlimonene sample was treated with approximately 2.3% w/w 2-oxovalericacid. The results are shown below in FIG. 3.

The first preparation, containing the lowest amount of the oxidizedlimonene sample was treated with approximately 3.9% w/w2-phenylglyoxylic acid. The results are shown below in FIG. 4.

Example 7: Formation of a Diammonium Salt Via the Reaction ofα-Ketoglutaric Acid (CAS #328-50-7) and N-Methyl Diethanolamine (NMDEA,CAS #105-59-9) in a 1:2 Molar Ratio

1.461 g (0.01 moles) of α-ketoglutaric acid was dissolved in 10 mL ofdry acetone to give a clear solution. This solution was added as oneportion to 2.384 g (0.02 moles) of neat NMDEA. The opaque, whiteemulsion was vortexed vigorously for 3-4 minutes, during which time asecond phase had coalesced. The mixture was placed in a freezer for atleast 30 minutes, causing the bottom phase to thicken to a waxy solid.While still cold, the top layer was easily removed via decantation orpipet, and discarded. Residual acetone was removed from the bottom,product layer via a stream of nitrogen followed by treatment in a vacuumoven at room temperature. This resulted in a clear, faint yellow, highlyviscous oil at room temperature containing the diammonium salt(AKG-DiNMDEA salt).

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of orange, grapefruit, and bergamot oils as the perfume oil.The mixed citrus oil was loaded into the solvent at approximately 19.4%v/v (6 mL oil into 25 mL solvent). Approximately 400 mg (2.0% w/v) ofthe AKG-DiNMDEA salt was dissolved in 20 mL of the mixed citrus perfume,and POV measurements were taken as a function of time after theaddition. An untreated perfume sample was handled similarly to thetreated perfume and also tested, because the POV can rise rapidly withhandling of the sample (opening the bottle, agitation, etc.). Theresults are shown in the table below.

POV of Treated POV of Untreated Time in Minutes Perfume Perfume 0.012.39 mmol/L 12.39 mmol/L 70 8.07 — 90 6.16 — 1150 1.38 — 1165 1.06 —1180 0.85 — 1195, 1210 — 12.31, 13.60 1220 0.78 — 1400 — 13.38 1420 0.77— 1440 (24 hours) 0.79 —

These data show a reduction in the POV of approximately 94%, 24 hoursafter addition of the AKG-DiNMDEA salt.

In addition to the treatment done in a model perfume as described above,a similar experiment was done in mixed citrus oil. A sample of mixedcitrus oil was made by combining lime, orange, grapefruit, lemon,mandarin, tangerine, and bergamot oils, so that a variety of terpenehydroperoxides would be present in the treated mixture being tested.Approximately 200 mg (1.0% w/v) of the AKG-DiNMDEA salt was added to 20mL of the mixed citrus oil. The salt did not appear to dissolvecompletely even after vigorous mixing. Nonetheless, POV measurementswere taken as a function of time after the addition. An untreated mixedcitrus oil sample was handled similarly to the treated oil and alsotested, because the POV can rise rapidly with handling of the sample(opening the bottle, agitation, etc.). The results are shown in thetable below.

POV of Treated POV of Untreated Time in Minutes Perfume Perfume 0.010.37 mmol/L 10.37 mmol/L 90 5.42 — 110 5.36 — 135 — 11.28 150 (2.5 hrs)4.87 — 1240 3.91 — 1250 4.40 — 1280 3.96 — 1505 (25 h & 5 min) 4.52 —1545 4.25 —

This represents only a moderate-to-good improvement in the POV status ofthe oil; a 59% reduction in POV after over a day of treatment time. Thisis likely due to the poor solubility of the 2-oxoacid salt in the citrusoil.

Example 8: Formation of a Diammonium Salt Via the Reaction ofα-Ketoglutaric Acid (CAS #328-50-7) and N,N-Dimethyldodeclyamine(DiMeC12A, CAS #112-18-5) in a 1:2 Molar Ratio

1.461 g (0.01 moles) of α-ketoglutaric acid was dissolved in 6 mL of dryacetone. This solution was added dropwise with stirring over the courseof 1-2 minutes to a separate solution of 4.268 g (0.02 moles) of N, Ndimethyldodecylamine in 6 mL of dry acetone. No visible indication ofreaction was seen except that the combined solution warmed up to about35-40° C. The mixture was shaken briefly but vigorously, and cooled in afreezer for 30 minutes. Even when cold, still no precipitation ofproduct occurred, but when the mixture was shaken again, the entire massalmost instantly solidified into a solid, white, waxy substance. Thissolid was warmed up to 30-35° C. to re-liquefy the product so thatentrapped acetone could be removed via a stream of nitrogen followed bytreatment in a vacuum oven at room temperature. This gave a white, waxysolid containing the diammonium salt (AKG-DiMeC12A salt).

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of orange, grapefruit, and bergamot oils as the perfume oil.The mixed citrus oil was loaded into the solvent at approximately 19.4%v/v (6 mL oil into 25 mL solvent). Approximately 400 mg (2.0% w/v) ofthe AKG-DiMeC12A salt was dissolved in 20 mL of the mixed citrusperfume, and POV measurements were taken as a function of time after theaddition. An untreated perfume sample was handled similarly to thetreated perfume and also tested, because the POV can rise rapidly withhandling of the sample (opening the bottle, agitation, etc.). Theresults are shown in the table below.

POV of Treated POV of Untreated Time in Minutes Perfume Perfume 0.012.74 mmol/L 12.74 mmol/L 35 8.31 — 45 8.35 — 70 6.77 — 130 6.54 — 1455.82 — 180 4.89 — 210 4.51 — 240 (4 hours) 4.15 — 270 3.49 — 4320 (3days, 72 hours) 0.0 indistinguishable 14.43 from blank

In addition to the treatment done in a model perfume as described above,a similar experiment was done in mixed citrus oil. A sample of mixedcitrus oil was made by combining lime, orange, grapefruit, lemon,mandarin, tangerine, and bergamot oils, so that a variety of terpenehydroperoxides would be present in the treated mixture being tested.Approximately 200 mg (1.0% w/v) of the AKG-DiMeC12A salt was dissolvedin 20 mL of the mixed citrus oil, and POV measurements were taken as afunction of time after the addition. An untreated mixed citrus oilsample was handled similarly to the treated oil and also tested, becausethe POV can rise rapidly with handling of the sample (opening thebottle, agitation, etc.). The results are shown in the table below.

Time in Minutes POV of Treated Perfume POV of Untreated Perfume 0.0 9.53mmol/L 9.53 mmol/L 90 3.32 — 95 2.32 — 105 2.63 — 130 2.68 — 150 (2.5hours) 2.28 — 250 1.81 — 260 1.41 — 4320 1.50 13.58 (3 days, 72 hours)

These data represent an 89.0% reduction in the POV, within 72 hours (3days) after the addition of AKG-DiMeC12A. It appears that theAKG-DiMeC12A may have been depleted after the 260 minute time point,because no further reaction happened even after an extended period.

Surface Tension Measurements of Aqueous AKG-DiMeC12A:

In order to evaluate the surfactant properties of AKG-DiMeC12A, thereduction in surface tension that it causes in aqueous solution versuspure water was measured. The measurement was made on a Kruss DSA100STensiometer by the pendant drop method. A 0.14 weight % solution ofAKG-DiMeC12A in water was used for the measurement. This concentrationwas chosen so the results could be compared to the literature value forknown surfactant sodium dodecyl sulfate (SDS) at 5 mM, which isapproximately 0.15 weight %. The results show that AKG-DiMeC12A hassignificant surfactant properties:

-   -   Pure water—71.57 mN/m    -   AKG-DiMeC12A—32.08 mN/m

For comparison, SDS at 5 mM concentration (approximately 0.15 weight %,which is very close to the 0.14 weight % used here) at 273K, has anair-water surface tension in the range of 33.5 to 35.5 mN/m depending onthe pH (see Hemainz, F. et al, Colloids Surf. A, 2002, 196, 19-24).

Example 9: Formation of a Diammonium Salt Via the Reaction ofα-Ketoglutaric Acid and (CAS #328-50-7) and 2-(dimethylamino(ethanol(Deanol, CAS #108-01-0) in a 1:2 Molar Ratio

1.461 g (0.01 moles) of α-ketoglutaric acid was dissolved in 10 mL ofdry acetone to give a clear solution. This solution was added over thecourse of 1-2 minutes with stirring to 1.783 g (0.02 moles) of neat 2dimethylaminoethanol (“Deanol”). The opaque, white emulsion was vortexedvigorously for a minute, during which time a second phase had coalesced.The mixture was placed in a freezer overnight, causing the bottom phaseto thicken to extremely viscous, hazy oil. While still cold, the toplayer was easily removed via decantation or pipet, and discarded.Residual acetone was removed from the bottom product layer via a streamof nitrogen followed by treatment in a vacuum oven at room temperature.This produced clear, colorless, viscous oil at room temperaturecontaining the diammonium salt (AKG DiDeanol salt).

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of orange, grapefruit, and bergamot oils as the perfume oil.The mixed citrus oil was loaded into the solvent at approximately 19.4%v/v (6 mL oil into 25 mL solvent). Approximately 200 mg (1.0% w/v) ofthe AKG DiDeanol salt was dissolved in 20 mL of the mixed citrusperfume, and POV measurements were taken as a function of time after theaddition. An untreated perfume sample was handled similarly to thetreated perfume and also tested, because the POV can rise rapidly withhandling of the sample (opening the bottle, agitation, etc.). Theresults are shown in the table below.

Time in Minutes POV Treated Perfume POV Untreated Perfume 45 — 11.73mmol/L 60 5.95 mmol/L — 75 5.66 — 115 4.96 — 195 3.20 — 210 3.08 — 270 —12.25 300 (5 hours) 2.31 — 370 1.73 — 380 1.72 — 390 — 11.70 1440 (24hours) 0.0 indistinguishable from 11.79 blank

Example 10: Formation of an Ammonium Salt Via the Reaction of PyruvicAcid (CAS #328-50-7) and N-Methyl Diethanolamine (NMDEA, CAS #105-59-9)in a 1:1 Molar Ratio

2.642 g (0.03 moles) of pyruvic acid was dissolved in 5 mL of dryacetone to give a clear solution. This solution was added dropwise withstirring over the course of 1-2 minutes to a second solution made from3.575 g (0.03 moles) of NMDEA and 5 mL of dry acetone. The resultingmixture became warm (approximately 35-45° C.) and hazy as the acidsolution was added. The milky emulsion was vortexed vigorously for aminute, during which time a second phase had coalesced. The mixture wasplaced in a freezer for at least 1 hour, causing the bottom phase toincrease significantly in viscosity, but not solidify. While still cold,the top layer was easily removed via decantation or pipet, anddiscarded. Residual acetone was removed from the bottom product layervia a stream of nitrogen followed by treatment in a vacuum oven at roomtemperature. This gave clear, golden colored, highly viscous oil at roomtemperature containing the diammonium salt (PA-NMDEA salt).

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of lime, orange, grapefruit, and bergamot oils as the perfumeoil. The mixed citrus oil was loaded into the solvent at approximately16.7% v/v (40 mL oil into 200 mL solvent, 240 mL total perfume).Approximately 150 mg (1.0% w/v) of the PA-NMDEA salt was dissolved in 15mL of the mixed citrus perfume, and POV measurements were taken as afunction of time after the addition. An untreated perfume sample washandled similarly to the treated perfume and also tested, because thePOV can rise rapidly with handling of the sample (opening the bottle,agitation, etc.). The results are shown in the table below.

Time in Hours POV Treated Perfume POV Untreated Perfume 0.0 — 5.55mmol/L 1.8 3.48 mmol/L — 71.5 1.01 — 72.5 — 6.66 73.3 0.58 — 74.7 — 6.58

These data suggest that the PA-NMDEA was depleted at the 73.3 hour mark,because the POV of the sample never went any lower after that, even atextended reaction times. This represents >90% reduction in POV; theaverage untreated oil after 3 days was (6.66+6.58)/2=6.62 mmol/L, so0.58/6.62×100=8.76% remaining, or 91.2% reduction in POV).

Example 11: Formation of an Ammonium Salt Via the Reaction ofPhenylglyoxylic Acid (PhGA, CAS #611-73-4) and N-Methyl Diethanolamine(NMDEA, CAS #105-59-9) in a 1:1 Molar Ratio

1.501 g (0.01 moles) of PhGA was dissolved in 5 mL of dry acetone togive a clear solution. This solution was added in one portion to asecond solution made from 1.192 g (0.01 moles) of NMDEA and 5 mL of dryacetone. The resulting mixture became warm (approximately 30-35° C.) andturned pale yellow in color, but no haze or precipitate formed. Thesolution was vortexed vigorously for a minute, and placed in a freezerfor 30 minutes. Still no precipitate or second layer formed, but thesolution was apparently supersaturated. An attempt was made to removethe solvent acetone via a stream of nitrogen, but almost instantly asthe nitrogen stream touched the solution, a thick paste of whitecrystalline material formed. The crystals began to re-dissolve back intothe acetone as the mixture warmed to room temperature. The product wasre-frozen, causing re-precipitation of the highly crystalline product,and the supernatant acetone was removed while still cold via pipet asmuch as possible. Residual acetone was then removed under a stream ofnitrogen to give pure white, needle shaped crystals. The crystallineproduct containing the diammonium salt (PhGA-NMDEA salt) was extremelyhygroscopic, and would liquefy very rapidly if exposed to ambientatmosphere; the white mass of needles had to be kept under vacuum or arigorous nitrogen blanket to remain crystalline. A weight/yield was notobtained due to the hygroscopicity.

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of lime, orange, grapefruit, and bergamot oils as the perfumeoil. The mixed citrus oil was loaded into the solvent at approximately16.7% v/v (40 mL oil into 200 mL solvent, 240 mL total perfume).Approximately 150 mg (1.0% w/v) of the PhGA-NMDEA salt was dissolved in15 mL of the mixed citrus perfume, and POV measurements were taken as afunction of time after the addition. An untreated perfume sample washandled similarly to the treated perfume and also tested, because thePOV can rise rapidly with handling of the sample (opening the bottle,agitation, etc.). The results are shown in the table below.

Time in Hours POV Treated Perfume POV Untreated Perfume  0.0 — 5.55mmol/L  1.8 4.87 mmol/L — 71.5 (~3 days)  4.61 — 72.5 — 6.66 73.3 4.18 —74.7 — 6.58  243 (~10 days) 2.62 8.37

These data suggest that while the phenylglyoxylic acid moiety does workto lower the POV in the model perfume, it is less reactive than thenon-aryl pyruvates studied. This difference in reactivity may be usefulin some circumstances.

Example 12: Reduction of POV in Sunflower Oil According to One AspectPresented Herein Using 2-Oxovaleric Acid

25 mL of sunflower oil (from an off-the-shelf, opened 1 quart containerwith approximately 25% atmospheric headspace; storage time unknown) wasplaced in a 30 mL vial at room temperature. 250 μL of 2-oxovaleric acidwas added. The vial was shaken and allowed to stand at ambienttemperature in laboratory lighting on the benchtop. No further treatmentwas done prior to the POV testing.

POV measurements were made on the sunflower oil before and after the2-oxovaleric acid treatment. The untreated oil was also re-measuredperiodically for comparison, since opening of the bottle replenishesatmospheric headspace and can cause the POV of the bottle contents torise. The % reduction was always calculated versus the most recent POVvalue on the untreated oil, and if multiple measurements were made, anaveraged value (shown in parentheses) was used for the calculation. Theresults are shown in the table below.

Time (in varying units) since addition of POV 2-oxovaleric acid POV (inmmol/L) reduction (in %) Untreated (time 0) 9.00, 8.68, 8.74 (8.81) N/A30 minutes 7.38 16.2 50 minutes 7.84 11.0 23 hours 4.95, 4.67 (4.81)45.4 Untreated (46 hours) 11.87, 10.35 (11.11) N/A 46 hours 5.34, 5.10(5.22) 53.0 Untreated (15 days) 11.89, 12.16, 12.85 (12.30) N/A 15 days2.27, 2.05, 1.99 (2.10) 82.9 N/A = Not applicable

The untreated sunflower oil increased in POV by nearly 40% (12.30/8.81mmol/L×100=139.6%) from merely sitting at room temperature in the bottlefor 15 days, with a headspace that had been replenished with ambientatmosphere during the brief opening required to do each sampling.

Conversely, the treatment of sunflower oil with 0.83% v/v of2-oxovaleric acid resulted in a 82.9% reduction in POV after 15 daysversus the untreated oil.

Example 13: Formation of an Ammonium Salt Via the Reaction ofPhenylpyruvic Acid (CAS #156-06-9) and N, N-Dimethyldecylamine(DiMeC10A, CAS #1120-24-7) in a 1:1 Molar Ratio

3.707 g (0.02 moles) of phenylpyruvic acid was dissolved in 10 mL of dryacetone to give a clear solution. A separate solution was made from3.283 g (0.02 moles) of N,N-dimethyldecylamine in 10 mL of dry acetone.The amine solution was added dropwise with stirring over the course of2-3 minutes to the phenylpyruvic acid solution; no visible indication ofreaction was seen, and no warming was noticeable. The mixture was shakenbriefly but vigorously, and cooled in a freezer for 30 minutes. A thicknetwork of white, flocculent, fine crystals was formed, and a smallamount of acetone was decanted off of the solid mass while still coldand discarded. The majority of the solvent acetone appeared entrappedwithin the crystalline network and was removed via a stream of nitrogenfollowed by treatment in a vacuum oven at room temperature. This gave aslightly off-white, fluffy crystalline solid in quantitative yield.

Reduction of POV in Sunflower Oil According to One Aspect PresentedHerein Using the Diammonium Salt Formed Via the Reaction ofPhenylpyruvic Acid and N, N-Dimethyldecylamine (Referred to Herein asDiMeC10A-PhPA):

15 mL of sunflower oil that had been stored in a plastic bottle at roomtemperature for 1 year, but never opened during this storage period, wasplaced into a 30 mL glass vial, and 0.3032 g of DiMeC10A-PhPA was addedto it. The majority of the salt dissolved, but some undissolved solidremained. The mixture was allowed to stand on the benchtop in ambientlaboratory light at room temperature, and POV measurements were takenperiodically. The results are shown in the table below.

Time since addition POV (mmol/L) of POV (mmol/L) % Reduction ofDiMeC10A-PhPA untreated oil of treated oil in POV  55 minutes 16.55 3.7877.2%   140 minutes — 0.00(*) 100% 1320 mins (22 hrs) 16.57 0.00(*) 100% 23 days 18.65 0.00(*) 100% (*)Indistinguishable from BLANK

This phenyl pyruvate salt produced extremely rapid reduction of thesunflower oil POV.

Reduction of POV in a Model Perfume According to One Aspect PresentedHerein Using the Diammonium Salt Formed Via the Reaction ofPhenylpyruvic Acid and N, N-Dimethyldecylamine (Referred to Herein asDiMeC10A-PhPA):

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of lime, orange, grapefruit, and bergamot oils as the perfumeoil. The mixed citrus oil was loaded into the solvent at approximately16.7% v/v (40 mL oil into 200 mL solvent, 240 mL total perfume).Approximately 164 mg (1.1% w/v) of the PhPA-DiMeC10A salt was dissolvedin 15 mL of the mixed citrus perfume, and POV measurements were taken asa function of time after the addition. An untreated perfume sample washandled similarly to the treated perfume and also tested, because thePOV can rise rapidly with handling of the sample (opening the bottle,agitation, etc.). The results are shown in the table below.

Time in Hours/ Days POV of Treated Perfume POV of Untreated Perfume 0.09.44 mmol/L 9.44 mmol/L 0.5 hours 5.7 — 1 hour — 9.8 4 hours 4.58 9.8 1day 3.1 9.66 2 days 2.38 10.60 4 days 1.98 10.12 7 days 1.33 10.38

The results shown above represent a 87.2% reduction in POV relative tountreated material 7 days after addition of PhPA-DiMeC10A.

Example 14: Formation of an Ammonium Salt Via the Reaction ofα-Oxo-2-Furanacetic Acid (CAS #1467-70-5) and N, N-Dimethyldecylamine(DiMeC10A, CAS #1120-24-7) in a 1:1 Molar Ratio

2.114 g (0.015 moles) of alpha-oxo-2-furanacetic acid was dissolved in10 mL of dry acetone. The alpha-oxo-2-furanacetic acid was used asreceived from the supplier (a greyish-tan colored crystalline solid),and gave a dark brown solution containing a small quantity ofundissolved flocculent material. It was decided to proceed with the “asis” material for preliminary screening, and a purified starting materialcould be made at a later time if the screening results so indicated.

A separate solution was made from 2.780 g (0.015 moles) ofN,N-dimethyldecylamine in 10 mL of dry acetone. The amine solution wasadded dropwise with stirring over the course of 5 minutes to the crudealpha-oxo-2-furanacetic acid solution; no visible indication of reactionwas seen, and no warming was noticeable. The mixture was shaken brieflybut vigorously, and cooled in a freezer for 30 minutes. Even when cold,still no precipitation of product occurred, so the acetone was removedvia a stream of nitrogen followed by treatment in a vacuum oven at roomtemperature. This gave brown, viscous oil in quantitative yield thatcrystallized to a tan solid after standing at freezer temperature forseveral days.

Reduction of POV in Sunflower Oil According to One Aspect PresentedHerein Using the Diammonium Salt Formed Via the Reaction ofalpha-oxo-2-furanacetic Acid and N, N-Dimethyldecylamine (Referred toHerein as FAA-DiMeC10A):

15 mL of sunflower oil that had been stored in a plastic bottle at roomtemperature for 1 year, but never opened during this storage period, wasplaced into a 30 mL glass vial, and 0.3358 g of FAA-DiMeC10A was addedto it. The majority of the salt dissolved, but a small amount of darkbrown insoluble droplets remained. The mixture was allowed to stand onthe benchtop in ambient laboratory light at room temperature, and POVmeasurements were taken periodically. The results are shown in the tablebelow.

Time since addition POV (mmol/L) of POV (mmol/L) of % Reduction ofFAA-DiMeC10A untreated oil treated oil in POV  85 minutes 16.55 5.1668.8%  140 minutes — 2.97 82.1% 1320 mins (22 hrs) 16.57 0.43 97.4%  23days 18.65 0.00(*)  100% (*)Indistinguishable from BLANK

Reduction of POV in a Model Perfume According to One Aspect PresentedHerein Using the Diammonium Salt Formed Via the Reaction ofAlpha-Oxo-2-Furanacetic Acid and N, N-Dimethyldecylamine (Referred toHerein as FAA-DiMeC10A):

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of lime, orange, grapefruit, and bergamot oils as the perfumeoil. The mixed citrus oil was loaded into the solvent at approximately16.7% v/v (40 mL oil into 200 mL solvent, 240 mL total perfume).Approximately 150 mg (1.0% w/v) of the FAA-DiMeC1 OA salt was dissolvedin 15 mL of the mixed citrus perfume, and POV measurements were taken asa function of time after the addition. An untreated perfume sample washandled similarly to the treated perfume and also tested, because thePOV can rise rapidly with handling of the sample (opening the bottle,agitation, etc.). The results are shown in the table below.

Time in Days POV of Treated Perfume POV of Untreated Perfume 0.0 — 5.15mmol/L 1 5.06 mmol/L 6.31 2 4.89 6.77 4 4.68 7.14 7 4.28 7.13

The results shown above represent a 40.0% reduction in POV relative tountreated material 7 days after addition of FAA-DiMeC1 OA. It appearsthat while the α-oxo-2-furanacetic acid moiety does work to lower thePOV in the model perfume, it is less reactive/slower than the non-arylα-oxocarboxylic acids studied.

Example 15: Formation of a Diammonium Salt Via the Reaction ofα-Ketoglutaric Acid (CAS #328-50-7) andtris[2-(2-(methoxyethoxy)ethyl]amine (CAS #70384-51-9) in a 1:2 MolarRatio

2.922 g (0.02 moles) of alpha-ketoglutaric acid was dissolved in 10 mLof dry acetone. A separate solution was made from 12.937 g (0.04 moles)of tris[2-(2-(methoxyethoxy)ethyl]amine (TMEEA) in 5 mL of dry acetone.The amine solution was added dropwise with stirring over the course of 2minutes to the AKG solution; no visible indication of reaction was seen,but the resulting mixture became slightly warm (approximately 35-45°C.). The mixture was shaken briefly but vigorously, and cooled in afreezer for 30 minutes. Even when cold, still no precipitation ofproduct occurred, so the acetone was removed via a stream of nitrogenfollowed by treatment in a vacuum oven at room temperature. This gave aclear, golden-brown colored, slightly viscous oil in quantitative yield.

Reduction of POV in Sunflower Oil According to One Aspect PresentedHerein Using the Diammonium Salt Formed Via the Reaction ofAlpha-Ketoglutaric Acid and tris[2-(2-(methoxyethoxy)ethyl]amine(Referred to Herein as AKG-diTMEEA):

15 mL of sunflower oil that had been stored in a plastic bottle at roomtemperature for 1 year, but never opened during this storage period, wasplaced into a 30 mL glass vial, and 0.5081 g of AKG-diTMEEA was added toit. The higher than usual weight of this compound was used because ofits' very high molecular weight (792.96 g/mole). This salt dissolvedtotally to give a clear, golden-brown oil. The solution was allowed tostand on the benchtop in ambient laboratory light at room temperature,and POV measurements were taken periodically. The results are shown inthe table below.

Time since addition POV (mmol/L) of POV (mmol/L) of % Reduction ofAKG-diTMEEA untreated oil treated oil in POV  65 minutes 16.55 11.7229.2%  180 mins (3 hrs) — 9.19 44.5% 1320 mins (22 hrs) 16.57 5.80 65.0% 23 days 18.65 2.10 88.7%

Example 16: Formation of a Diammonium Salt Via the Reaction ofα-Ketoglutaric Acid (CAS #328-50-7) and N, N-Dimethyldodecylamine (CAS#112-18-5) in a 1:2 Molar Ratio

1.461 g (0.01 moles) of alpha-ketoglutaric acid was dissolved in 6 mL ofdry acetone. This solution was added dropwise with stirring over thecourse of 1-2 minutes to a separate solution of 4.268 g (0.02 moles) ofN,N-dimethyldodecylamine in 6 mL of dry acetone. No visible indicationof reaction was seen except that the combined solution warmed up toabout 35-40° C. The mixture was shaken briefly but vigorously, andcooled in a freezer for 30 minutes. Even when cold, still noprecipitation of product occurred, but when the mixture was shakenagain, the entire mass almost instantly solidified into a solid, white,waxy substance. This solid was warmed up to 30-35° C. to re-liquefy theproduct so that entrapped acetone could be removed via a stream ofnitrogen followed by treatment in a vacuum oven at room temperature.This gave a white, waxy solid in quantitative yield.

Reduction of POV in Sunflower Oil According to One Aspect PresentedHerein Using the Diammonium Salt Formed Via the Reaction ofAlpha-Ketoglutaric Acid and N,N-Dimethyldodecylamine (Referred to Hereinas AKG-DiMeC12A):

15 mL of sunflower oil that had been stored in a plastic bottle at roomtemperature for 1 year, but never opened during this storage period, wasplaced into a 30 mL glass vial, and 0.3062 g of AKG-DiMeC12A was addedto it. This salt did not dissolve totally, but gave a hazy, gel-likesuspension with the sunflower oil. The mixture was allowed to stand onthe benchtop in ambient laboratory light at room temperature, and POVmeasurements were taken periodically. The results are shown in the tablebelow.

Time since addition POV (mmol/L) of POV (mmol/L) of % Reduction ofAKG-DiMeC12A untreated oil treated oil in POV  50 minutes 16.55 15.367.2% 1320 mins (22 hrs) 16.57 12.68 23.5%  23 days 18.65 3.05 83.6%

Example 17: Formation of an Ammonium Salt Via the Reaction of PyruvicAcid (CAS #127-17-3) and N-Methyl Diethanolamine (NMDEA, CAS #105-59-9)in a 1:1 Molar Ratio

2.642 g (0.03 moles) of pyruvic acid was dissolved in 5 mL of dryacetone to give a clear solution. This solution was added dropwise withstirring over the course of 1-2 minutes to a second solution made from3.575 g (0.03 moles) of NMDEA and 5 mL of dry acetone. The resultingmixture became warm (approximately 35-45° C.) and hazy as the acidsolution was added. The milky emulsion was vortexed vigorously for aminute, during which time a second phase had coalesced. The mixture wasplaced in a freezer for at least 1 hour, causing the bottom phase toincrease significantly in viscosity, but not solidify. While still cold,the top layer was easily removed via decantation or pipet, anddiscarded. Residual acetone was removed from the bottom product layervia a stream of nitrogen followed by treatment in a vacuum oven at roomtemperature. This gave clear, golden colored, highly viscous oil at roomtemperature in quantitative yield.

Reduction of POV in Sunflower Oil According to One Aspect PresentedHerein Using the Diammonium Salt Formed Via the Reaction of Pyruvic Acidand N-Methyl Diethanolamine (Referred to Herein as PA-NMDEA):

15 mL of sunflower oil that had been stored in a plastic bottle at roomtemperature for 1 year, but never opened during this storage period, wasplaced into a 30 mL glass vial, and 0.2988 g of PA-NMDEA was added toit. This salt appeared to dissolve and/or disperse, but the resultingmixture was not totally clear; it had a translucent, colloidalappearance. The mixture was allowed to stand on the benchtop in ambientlaboratory light at room temperature, and POV measurements were takenperiodically. The results are shown in the table below.

Time since addition POV (mmol/L) of POV (mmol/L) of % Reduction ofPA-NMDEA untreated oil treated oil in POV  75 minutes 16.55 15.79 4.6% 185 minutes — 12.34 25.4% 1320 mins (22 hrs) 16.57 13.24 20.1%  23 days18.65 11.67 37.4%

Example 18: Reduction of POV in a Model Perfume According to One AspectPresented Herein Using α-Ketoglutaric Acid

α-ketoglutaric acid is a strong acid, wherein a solution of 0.114 g ofα-ketoglutaric acid in 10 mL of water had a measured pH of 1.75.Consequently, the amount of the α-ketoglutaric acid in solution in ahydroalcoholic perfume base may have to be limited, to preventalterations of the organoleptic properties on the perfume raw materials.

A model perfume was made using 90/10 v/v ethanol/water as a solvent, towhich, a mixture of orange, grapefruit, and bergamot oils was added. Themixed citrus oil was loaded into the solvent at approximately 19.4% v/v(6 mL oil into 25 mL solvent). Approximately 240 mg (1.2% w/v) ofα-ketoglutaric acid was dissolved in 20 mL of the mixed citrus perfume,and a POV measurement was taken the following day. The results are shownin the table below.

Time in Minutes POV of Treated Perfume POV of Untreated Perfume 0.011.99 mmol/L 11.99 mmol/L 1440 (24 hours) 0.0 indistinguishable — fromblank

These data show a complete reduction in the POV of the formulatedperfume 24 hours after treatment of the formulated perfume withα-ketoglutaric acid.

Example 19: Reduction of POV in a Model Perfume According to One AspectPresented Herein Using Oxaloacetic Acid

Oxaloacetic acid is known to be unstable in aqueous solutions (see H. A.Krebs, Biochemistry (1942) 36, 303-305), leading to evolution of carbondioxide and pyruvic acid. Nonetheless, oxaloacetic acid is effective inreducing the POV in solutions that will solubilize it (for example,hydroalcoholic perfumes). However, it is unclear whether the POVreduction occurs via oxaloacetic acid directly, or via liberated pyruvicacid, or both. An analysis of the reaction products (acetic acid versusmalonic acid) could distinguish the two pathways, but this was notpursued here.

A model perfume was made using 90/10 v/v ethanol/water as a solvent, towhich, a mixture of orange, grapefruit, and bergamot oils was added. Themixed citrus oil was loaded into the solvent at approximately 19.4% v/v(6 mL oil into 25 mL solvent). Approximately 166 mg (0.83% w/v) ofoxaloacetic acid was dissolved in 20 mL of the mixed citrus perfume, andPOV measurements were taken at the times indicated in the table below.

Time in Minutes POV of Treated Perfume POV of Untreated Perfume 0.0 9.44mmol/L 9.44 mmol/L 27 5.90 — 245 1.91 — 1440 (24 hours) 0.0indistinguishable — from blank

These data show a complete reduction in the POV of the formulatedperfume 24 hours after treatment of the formulated perfume withoxaloacetic acid.

Example 20: Formation of an Ammonium Salt Via the Reaction ofPhenylglyoxylic Acid (CAS #611-73-4) and1-(2-hydroxyethyl)-2-imidazolidinone (HEI, CAS #3699-54-5) in a 1:1Molar Ratio

3.003 g (0.02 moles) of phenylglyoxylic acid was dissolved in 10 mL ofdry acetone to give a clear solution. A separate solution was made from2.603 g (0.02 moles) of 1-(2-hydroxyethyl)-2-imidazolidinone in 10 mL ofdry acetone. Since 1-(2-hydroxyethyl)-2-imidazolidinone was supplied asa 75% w/w solution in water, the actual amount of the 75% reagent usedwas 3.471 g to compensate for the weight of solvent water. The1-(2-hydroxyethyl)-2-imidazolidinone amine solution was added dropwisewith stirring over the course of 3 minutes to the phenylglyoxylic acidsolution; no visible indication of reaction was seen, and no warming wasnoticeable. The mixture was shaken briefly but vigorously, and cooled ina freezer for 30 minutes. Even when cold, still no precipitation ofproduct occurred, so the acetone solvent was removed via a stream ofnitrogen followed by treatment in a vacuum oven at room temperature.This gave clear, pale yellow, highly viscous oil in quantitative yield.

Reduction of POV in Model Perfume According to One Aspect PresentedHerein Using the Diammonium Salt Formed Via the Reaction ofPhenylglyoxylic Acid and 1 (2 hydroxyethyl)-2-imidazolidinone (Referredto Herein as PhGA-HEI):

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of lime, orange, grapefruit, and bergamot oils as the perfumeoil. The mixed citrus oil was added into the solvent at approximately16.7% v/v (40 mL oil into 200 mL solvent, 240 mL total perfume).Approximately 150 mg (1.0% w/v) of the PhGA-HEI salt was dissolved in 15mL of the mixed citrus perfume, and POV measurements were taken as afunction of time after the addition. An untreated perfume sample washandled similarly to the treated perfume and also tested, because thePOV can rise rapidly with handling of the sample (opening the bottle,agitation, etc.). The results are shown in the table below.

Time in Days POV of Treated Perfume POV of Untreated Perfume 0.0 — 5.15mmol/L 1 3.51 mmol/L 6.31 2 3.18 6.77 4 3.06 7.14 7 2.94 7.13

The results shown above represents a 58.8% reduction in POV relative tountreated material 7 days after addition of PhGA-HEI. It appears thatwhile the phenylglyoxylic acid moiety does work to lower the POV in themodel perfume, it is less reactive/slower than the non-arylα-oxocarboxylic acids studied. This difference in reactivity may beuseful in some circumstances.

Example 21: Formation of a Diammonium Salt Via the Reaction ofα-Ketoglutaric Acid (CAS #328-50-7) and1-(2-hydroxyethyl)-2-imidazolidinone (HEI, CAS #3699-54-5) in a 1:2Molar Ratio

2.922 g (0.02 moles) of alpha-ketoglutaric acid (AKG) was dissolved in10 mL of dry acetone to give a clear solution. A separate solution wasmade from 5.206 g (0.04 moles) of 1-(2-hydroxyethyl)-2-imidazolidinone(HEI) in 10 mL of dry acetone. Since HEI was supplied as a 75% w/wsolution in water, the actual amount of the 75% reagent used was 6.942 gto compensate for the weight of solvent water. The HEI amine solutionwas added dropwise with stirring over the course of 3 minutes to the AKGsolution; no visible indication of reaction was seen, and no warming wasnoticeable. The mixture was shaken briefly but vigorously, and cooled ina freezer for 1 hour. Even when cold, still no precipitation of productoccurred, so the acetone solvent was removed via a stream of nitrogenfollowed by treatment in a vacuum oven at room temperature. This gaveclear, water-white, extremely viscous oil in quantitative yield.

Reduction of POV in Model Perfume According to One Aspect PresentedHerein Using the Diammonium Salt Formed Via the Reaction ofα-Ketoglutaric Acid and 1 (2 hydroxyethyl)-2-imidazolidinone (Referredto Herein as AKG-HEI):

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of lime, orange, grapefruit, and bergamot oils as the perfumeoil. The mixed citrus oil was loaded into the solvent at approximately16.7% v/v (40 mL oil into 200 mL solvent, 240 mL total perfume).Approximately 150 mg (1.0% w/v) of the AKG-HEI salt was dissolved in 15mL of the mixed citrus perfume, and POV measurements were taken as afunction of time after the addition. An untreated perfume sample washandled similarly to the treated perfume and also tested, because thePOV can rise rapidly with handling of the sample (opening the bottle,agitation, etc.). The results are shown in the table below.

Time in Days POV of Treated Perfume POV of Untreated Perfume 0.0 — 5.15mmol/L 1 1.12 mmol/L 6.31 2 0.72 6.77 4 0.70 7.14 7 0.56 7.13

The results shown above represent a 92.1% reduction in POV relative tountreated material 7 days after addition of AKG-DiHEI.

Example 22: Formation of an Ammonium Salt Via the Reaction ofα-Ketoglutaric Acid (CAS #328-50-7) and N,N-Dimethyldodeclyamine(DiMeC12A, CAS #112-18-5) in a 1:1 Molar Ratio (Referred to Herein asAKG-Mono(DiMeC12A))

2.922 g (0.02 moles) of α-ketoglutaric acid was dissolved in 12 mL ofdry acetone. This solution was added dropwise with stirring over thecourse of 1-2 minutes to a separate solution of 4.268 g (0.02 moles) ofN, N-dimethyldodecylamine in 6 mL of dry acetone. The mixture wasshaken, but no visible indication of reaction was seen except that thecombined solution warmed up to about 35-40° C. The mixture remainedclear for a few minutes, but when shaken again, the entire massinstantly solidified into a solid white crystalline block. This solidwas warmed up to 30-35° C. to re-liquefy the product so that entrappedacetone could be removed via a stream of nitrogen followed by treatmentin a vacuum oven at room temperature. This gave a white, waxy solid inquantitative yield.

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of orange, grapefruit, and bergamot oils as the perfume oil.The mixed citrus oil was loaded into the solvent at approximately 19.4%v/v (6 mL oil into 25 mL solvent). Approximately 200 mg (1.0% w/v) ofthe AKG-monoMeC12A salt was dissolved in 20 mL of the mixed citrusperfume, and POV measurements were taken as a function of time after theaddition. An untreated perfume sample was handled similarly to thetreated perfume and also tested, because the POV can rise rapidly withhandling of the sample (opening the bottle, agitation, etc.). Theresults are shown in the table below.

Time in Minutes POV of Treated POV of Untreated (in Hours) PerfumePerfume 0.0 11.99 mmol/L 11.99 mmol/L 30 (0.5) 7.01 — 45 (0.75) 6.97 —60 (1.0) 7.02 — 180 (3.0) 4.89 — 210 (3.5) 4.54 — 240 (4.0) 3.78 — 270(4.5) 3.77 — 300 (5.0) 3.05 — 340 (5.67) 2.52 — 1440 (24 hours) 0.7611.66 1470 (24.5 hours) 0.67 — 1560 (26 hours) 0.0 indistinguishable —from blank

These data represent represents total and complete reduction in the POV,within 26 hours after the addition of AKG-mono(DiMeC12A).

In addition to the treatment done in a model perfume as described above,a similar experiment was done in mixed citrus oil. A sample of mixedcitrus oil was made by combining lime, orange, grapefruit, lemon,mandarin, tangerine, and bergamot oils, so that a variety of terpenehydroperoxides would be present in the treated mixture being tested.Approximately 200 mg (1.0% w/v) of the AKG-mono(DiMeC12A) salt was addedinto 20 mL of the mixed citrus oil, but a substantial portion of it didnot dissolve. POV measurements were taken as a function of time afterthe addition. An untreated mixed citrus oil sample was handled similarlyto the treated oil and also tested, because the POV can rise rapidlywith handling of the sample (opening the bottle, agitation, etc.). Theresults are shown in the table below.

Time in Minutes POV of Treated POV of Untreated (in Hours) PerfumePerfume 0.0 9.45 mmol/L 9.45 mmol/L 90 (1.5) 2.09 — 100 (1.67) 2.00 —120 (2.0) — 10.12 135 (2.25) 1.63 — 180 (3.0) 1.79 — 1320 (22.0) 0.9610.56 1345 (22.42) 0.91 — 1620 (27.0) — 10.42 1660 (27.67) 0.80 — 1680(28.0) 0.60 —

These data represent a 94.2% reduction in POV relative to untreatedmaterial 28.0 hours after addition of the AKG-mono(DiMeC12A) salt.

Surface Tension Measurements of Aqueous AKG-monoDiMeC12A:

In order to evaluate the surfactant properties of AKG-Mono(DiMeC12A),the reduction in surface tension that it causes in aqueous solutionversus pure water was measured. The measurement was made on a KrussDSA100S Tensiometer by the pendant drop method. A 0.14 weight % solutionof AKG-Mono(DiMeC12A) in water was used for the measurement. Thisconcentration was chosen so the results could be compared to theliterature value for known surfactant sodium dodecyl sulfate (SDS) at 5mM, which is approximately 0.15 weight %. The results show thatAKG-Mono(DiMeC12A) has significant surfactant properties:

-   -   Pure water—71.57 mN/m    -   AKG-monoDiMeC12A—32.93 mN/m

For comparison, SDS at 5 mM concentration (˜0.15 weight %, which is veryclose to the 0.14 weight % used here) at 273K, has an air-water surfacetension in the range of 33.5 to 35.5 mN/m depending on the pH (seeHernainz, F. et al, Colloids Surf. A, 2002, 196, 19-24).

Example 23: Formation of an Ammonium Salt Via the Reaction ofIndole-3-Pyruvic Acid (I-3-PA, CAS #392-12-1) and N-Methyldiethanolamine(NMDEA, CAS #105-59-9) in a 1:1 Molar Ratio

0.61 g (0.003 moles) of I-3-PA-NMDEA was placed in 4 mL of methanol, butit only partially dissolved. A separate mixture was made of 0.357 g(0.003 moles) of NMDEA in 2 mL of acetone, which formed a clearsolution. The amine solution was added in one portion to theindole-3-pyruvic acid and vortexed vigorously for 1 minute. There wassome solid that remained undissolved, so the mixture was placed in a 40°C. water bath. As it warmed, all the material dissolved to form a darkorange, clear solution. The mixture was allowed to cool to roomtemperature, but no precipitate formed. The solution was placed in afreezer for 30 minutes, during which time light pink needle-likecrystals had fallen out. The mother liquor was removed with a pipet; itwas shown to contain a substantial amount of lower purity material thatcould be further recovered by blowing down the solvent under a stream ofnitrogen to give a deep orange solid. For the purpose of preliminaryexperiments, the two portions of product were recombined pending thedevelopment of a more efficient crystallization procedure. The yield wasquantitative.

A model perfume was made using 90/10 v/v ethanol/water as a solvent, anda mixture of orange, grapefruit, and bergamot oils as the perfume oil.The mixed citrus oil was loaded into the solvent at approximately 19.4%v/v (6 mL oil into 25 mL solvent). Approximately 244 mg (1.2% w/v) ofthe I-3-PA-NMDEA salt was dissolved in 20 mL of the mixed citrusperfume, and POV measurements were taken as a function of time after theaddition. An untreated perfume sample was handled similarly to thetreated perfume and also tested, because the POV can rise rapidly withhandling of the sample (opening the bottle, agitation, etc.). Theresults are shown in the table below.

POV of Treated POV of Untreated Time in Minutes Perfume Perfume 0.011.09 mmol/L 11.09 mmol/L 60 0.0 indistinguishable — from blank

These data represent a rapid reduction in POV relative to untreatedmaterial 60 minutes after addition of the I-3-PA-NMDEA salt.

Example 24: Reduction of POV in a Model Perfume According to One AspectPresented Herein Using a Diammonium Salt Made from α-Ketoglutaric Acid(CAS #328-50-7) and N-Methyl Diethanolamine (NMDEA, CAS #105-59-9) in a1:2 Molar Ratio Incorporated on a Solid Support

It had been observed that a reduction of POV in citrus oils could beproduced even with α-oxocarboxylic acid salts that were practicallyinsoluble in the citrus oil being treated. It appeared that thisobservation held true for both solid salts and liquid salts (which tendto be of high viscosity), although the rate and efficiency of thereduction was not as high as that for soluble salts. It was hypothesizedthat the surface area of contact between the α-oxocarboxylic acid saltphase and the citrus oil phase was likely a limiting factor, so if true,any method of increasing the contact area should promote a more rapid,facile reaction.

Towards that goal, an attempt was made to spread a thin, highly disperselayer of the diammonium salt formed from α-ketoglutaric acid and twoequivalents of N-methyldiethanolamine (AKG-DiNMDEA) onto a chemicallyinert, high surface area solid support. In this example, a commerciallyavailable household scrubbing pad made of extremely thin stainless steel(a Scotch-Brite Scrubby® pad made by 3M Company) was used.

Preparation of an AKG-DiNMDEA Coated Pad:

A single pad was cleaned as follows: The pad was placed in a 250 mLglass beaker and covered completely with pentane. The beaker wassonicated for three minutes, the pentane drained, and the procedurerepeated with acetone. The acetone was also drained, and the pad driedin a vacuum oven at room temperature for one hour. The pad weighed19.229 g both before and after the cleaning procedure, so no discernableweight loss was observed as a result of the cleaning.

A solution was made from 3.0 g of AKG-DiNMDEA and 10 mL of fragrancegrade ethanol. The pad was loaded by spreading the solution over thestainless steel pad via pipet, and drying the ethanol off under vacuumat room temperature. This was best accomplished with the solution splitinto about three portions, with a drying step in between each; there wassome run-off when attempted in one portion, because the pad could notcompletely hold that much solution. When all the ethanol was removed,the viscous AKG-DiNMDEA appeared to cling to the pad tightly enough sothat the pad could be transferred between containers without loss of theliquid coating.

Treatment of Mixed Citrus Oil:

A sample of mixed citrus oil was made by combining lime, orange,grapefruit, and bergamot oils, so that a variety of terpenehydroperoxides would be present in the treated mixture being tested.Into two separate 250 mL glass bottles, 150 mL each of the mixed citrusoil was placed. This allowed for a significant atmospheric headspace tobe present in the closed bottles, which would be replenished by freshatmosphere/oxygen upon every opening of the bottle to withdraw analiquot for testing. This arrangement was designed to mimic the oxygenexposure resulting from typical handling in production of a drum ofcitrus oil raw material, and should lead to realistic levels ofautoxidation in the contained oils.

The AKG-DiNMDEA coated pad was placed in one of the bottles (the TreatedSample) and totally submerged under the mixed citrus oil therein. In thesecond bottle, nothing besides the mixed citrus oil was placed (theUntreated Sample). These bottles were allowed to stand on the laboratorybench under ambient temperature and lighting conditions throughout thetesting period. Periodically, an aliquot was withdrawn from each bottlefor POV testing. Downward flow of the coating off of the pad, asevidenced by the appearance of a puddle of AKG-DiNMDEA collecting at thebottom of the vessel, took several weeks to occur to a noticeableextent. The interphase contact area presumably became lower as this flowprogressed, likely reducing the efficiency of the reduction reaction.Nonetheless, significant protection of the treated citrus oil fromautoxidation-induced POV increase occurred, as reported below.

Recharge of the Pad:

After 26 days, it was observed that the POV of the Treated Sample beganto increase slightly (see FIG. 5). Simultaneously, the % POV reductionof Treated Sample relative to Untreated Sample began to decreaseslightly (see FIG. 6). This was interpreted to mean that the coated padhad stopped working effectively, perhaps because the AKG-DiNMDEA waschemically spent. Alternatively, perhaps the AKG-DiNMDEA, a viscousliquid, had flowed slowly downward off of the stainless steel coils ofthe pad. This would create a puddle with low surface area, and thereforethe reagent would become ineffective due to insufficient contact withthe citrus oil.

The pad was removed from the mixed citrus oil and washed in successionwith 100 mL each of acetone, then 95% ethanol, then acetone again. Thecleaned pad was dried under vacuum at room temperature, and reloadedwith AKG-DiNMDEA. A simpler procedure was tried this time torecharge/reactivate/reload the Scrubby®. Instead of applying a solutionand evaporating the solvent, the viscous AKG-DiNMDEA oil was simplyrubbed into the steel coils; approximately 3.2 g of AKG-DiNMDEA wasplaced onto the surface of the steel pad and kneaded in with glovedhands to distribute the oil as evenly as possible. Then the rechargedScrubby® was placed back into the container of treated citrus oil, andPOV monitoring was continued as before. The timepoint corresponding tothe recharge is shown by a vertical purple line in FIGS. 5 and 6.

Raw POV Titration Data:

Time since Scrubby Recharge Time in Treated with (in Days) DaysUntreated Scrubby 0.125 11.68 8.53 0.125 11.14 7.94 2.1 12.89 5.99 2.113.03 6.12 22 17.37 4.91 22 17.84 4.8 26 21.3 5.14 26 21.02 4.9 30 26.736.83 30 26.71 6.83 33 30.73 6.86 33 29.96 7.7 33 30.35 7.24 0.8 34 34.726.88 0.8 34 33.21 6.97 2.8 36 37.59 5.32 2.8 36 37.7 5.94 7 40 41.476.29 7 40 40.83 6.29 16 49 42.35 4.62 16 49 40.51 4.58 28 61 42.28 3.8928 61 42.44 3.72 Time since Scrubby Recharge Time in % Reduction of (inDays) Days POV 0.125 27.8 2.1 53.2 22 72.4 26 76.3 30 74.4 33 76 0.8 3479.6 2.8 36 85.1 7 40 84.7 16 49 88.9 28 61 91

Example 25: Reduction of POV in a Selection of Consumer ProductsAccording to One Aspect Presented Herein

This Example reports the treatment of exemplary consumer productformulations. The consumer product formulations had a measurable levelof oxidation as received, as shown in the table below, but the POVlevels were low except the all-purpose cleaner. All of the samples hadnot been fragranced, so the POV was be associated with autooxidized basecomponents. The five consumer product formulations were spiked with anextremely oxidized limonene that was produced in a photoreactor as asource of mixed limonene hydroperoxide isomers (the POV was 1434mmol/L). The oxidized limonene was spiked into each at a level of 10 μLper gram, so approximately 14.3 mmol/L of POV would be added to theexisting, as-received POV.

In all cases, the treatment with an α-oxocarboxylic acid ammonium saltproduced a rapid and extensive lowering of the sample's POV; thehydroperoxides present in the sample were consumed/destroyed via adefined, controlled reaction with the α-oxocarboxylic acid to yieldharmless and predictable by-products. In some cases, the untreatedsample showed a much slower but steady reduction in POV; this is likelydue to the limonene hydroperoxides reacting with and oxidizing basecomponents, to form unknown by-products. This may have deleteriouseffects on the formulation in many cases, such as malodor formation,discoloration, changes in physical properties, etc. Such uncontrolled,undirected lowering of POV will likely lower the skin sensitizingpotential of a sample due to consumption of sensitizing hydroperoxides,but is not necessarily positive to the formulation in all aspects.

POV of Consumer Product Samples as Received (Before Spike with OxidizedLimonene)

POV Amount of Consumer Products (mmol/L) Sample Titrated Notes #1. HandDishwashing 2.65 1 mL 1.0083 g, Viscous Liquid white liquid #2. Shampoo0.97 1 mL 0.9992 g, Viscous white liquid #3. All Purpose 7.30 1 mL0.9910 g, Mobile Spray Cleaner colorless liquid #4. Skin Cream 0 1.0332g Thick white cream #5. Antiperspirant 1.65 1.0766 g White semi-solidStick

Sample Preparation:

40 mL (Sample #3) or 40 g (Samples #1, 2, 4 & 5) were each spiked with0.4 mL of oxidized limonene and mixed until homogeneous. Half of eachspiked consumer product sample was transferred to a second container,and treated as described in the table below with 0.5-1% (w/w) of a2-oxocarboxylic acid ammonium salt, then mixed to homogeneity. Each ofthe five pairs of two samples, treated & un-treated, were allowed tostand on the benchtop in ambient laboratory light at room temperature,and POV measurements were taken periodically. The results are describedbelow.

Spiked Consumer 2-Oxocarboxylic Acid Ammonium Salt Used Product forTreatment (dosage and identification) #1. Hand 0.5% (w/w) ofPA-NMDEA:pyruvic acid + N-methyl Dishwashing diethanolamine, 1:1 molarratio Liquid Soap #2. Shampoo 0.5% (w/w) of PA-NMDEA:pyruvic acid +N-methyl diethanolamine, 1:1 molar ratio #3. All Purpose 1% (w/w) ofAKG-DiNMDEA:α-ketoglutaric acid + Spray Cleaner N-methyldiethanolamine,1:2 molar ratio #4. Skin Cream 1% (w/w) of AKG-DiMeC12A:α-ketoglutaricacid + N,N-dimethyldodecylamine, 1:2 molar ratio #5. Anti- 1% (w/w) ofAKG-diTMEEA:α-ketoglutaric acid + PerspirantTris[2-(2-(methoxyethoxy)ethyl]amine, 1:2 molar ratio Stick

Sample 1, Hand Dishwashing Liquid Soap (HDLS)—See FIGS. 7 and 8:

POV (mmol/L) POV (mmol/L) Time since addition of of untreated of treated% Reduction PA-NMDEA HDLS HDLS in POV 110 minutes 15.38 4.33 71.8% 280minutes (4.67 h) 14.89 2.54 82.9% 26 hrs 13.4 1.03 92.3% 4 days 11.010.65 94.1% 8 days 9.25 0.59 93.6% 15 days 7.6 0.62 91.8% 26 days 5.230.54 89.7%

Sample 2, Shampoo—See FIGS. 9 and 10:

POV (mmol/L) POV (mmol/L) Time since addition of of untreated of treated% Reduction PA-NMDEA Shampoo Shampoo in POV 120 minutes 13.69 12.0412.1% 280 minutes (4.67 h) 14.05 11.25 19.9% 26 hrs 13.91 9.53 31.5% 4days 13.15 7.18 45.4% 8 days 12.43 5.48 55.9% 15 days 11.41 4.01 64.9%26 days 10.2 2.55 75.0%

Sample 3, All Purpose Cleaner (APC)—See FIGS. 11 and 12:

POV (mmol/L) POV (mmol/L) Time since addition of of untreated of treated% Reduction AKG-DiNMDEA APC APC in POV 100 minutes 20.28 16.07 20.8% 260minutes (4.33 h) 20.62 14.1 31.6% 26 hrs 20.47 8.67 57.6% 4 days 19.844.99 74.8% 8 days 19.08 3.46 81.9% 15 days 17.32 2.27 86.9% 26 days15.57 1.44 90.8%

Sample 4, Skin Cream—See FIGS. 13 and 14:

POV (mmol/L) POV (mmol/L) Time since addition of of untreated of treated% Reduction AKG-DiMeC12A Skin Cream Skin Cream in POV 140 minutes 13.996.06 56.7% 300 minutes (5 h) 14.23 4.5 68.4% 26 hrs 13.52 2.08 84.6% 4days 12.8 1.16 90.9% 8 days 11.79 0.82 93.0% 15 days 11.51 0 100.0%

Sample 5, Antiperspirant Stick (APS)—See FIGS. 15 and 16:

Time since addition of POV (mmol/L) of POV (mmol/L) % ReductionAKG-DiTMEEA untreated APS of treated APS in POV 150 minutes 12.87 3.771.3% 310 minutes (5.17 h) 13.97 3.03 78.3% 26 hrs 14.64 2.46 83.2% 4days 12.57 2.04 83.8% 8 days 13.65 1.77 87.0% 8 days* 13.46 1.8 86.6% 15days 12.9 1.50 88.4% 26 days 12.55 1.42 88.7%

Example 26: Reduction of POV in a Selection of Essential Oils Obtainedfrom Non-Citrus Sources According to One Aspect Presented Herein

In this Example, a series of non-citrus-derived essential oils weretreated as described below with AKG-DiTMEEA (the diammonium salt madefrom alpha-ketoglutaric acid (AKG, CAS #328-50-7) andTris[2-(2-(methoxyethoxy)ethyl]amine (TMEEA, CAS #70384-51-9) in a 1:2molar ratio). The results indicate that the claimed treatment iseffective over a broad range of essential oils, which contain a broadrange of terpenes and other small organic molecules such as aromatics.Therefore a very broad range of organic hydroperoxides will be presentas autoxidation products in these other oil types, and they all appearto be reduced by 2-oxoacids (specifically an α-ketoglutarate ammoniumsalt in this case).

The data below shows nine oils along with the POV obtained on each asreceived from production stock. For each oil, 20 mL was placed inseparate 30 mL glass vials, and subjected to the following procedure for8 days on a daily basis; the vial was opened to refresh the atmosphericheadspace, then reclosed and shaken to maximize the gas/liquid contact,then stored on the benchtop under ambient laboratory temperature andlighting conditions. This procedure was designed to mimic the typicalhandling of a container in a production setting, in which the oil getsconsumed in many small aliquots, rather than an entire container at atime.

On Day 4, each oil sample was split in half, so two 10 mL aliquots wereplaced in separate vials to create a “Treated” and an “Untreated”sample. To the Treated sample of each oil type, AKG-DiTMEEA was added asper the Dosing chart below. The pine oil had an extremely high POV, sothe dosing and measurement protocol was somewhat different from theother oils. The daily opening, shaking, and standing procedure continuedfor another four days until the POV measurements were taken. It can beseen that 8 days of such handling of the untreated oils causedsignificant increases in POV measurement.

The Siberian Pine Oil, even as received, had a POV that was unusuallyhigh, to such a degree that stoichiometric depletion of the AKG-DiTMEEAis likely to occur. For this reason, two levels of AKG-DiTMEEA treatmentwere tried, ×2 and ×4 the treatment used on the other oils. The resultsindicate that even greater amounts may be necessary to completelyremediate this Pine Oil sample, because AKG-DiTMEEA has a high molecularweight due to the large amine groups, and there is a low stoichiometricability to scavenge hydroperoxides per unit weight. A different, lowermolecular weight 2-oxoacid salt may be a better choice.

POV of Untreated Oils, Before and after Handling:

POV (mmol/L) of untreated oils As Received After Handling Essential oils(Day 0) (Day 8) #1: Basil oil 10.56 23.88 #2: Coriander oil 13.23 23.60#3: Patchouli oil 2.42 4.89 #4: Star Anise oil 1.44 3.52 #5: Cinnamonleaf oil 2.60 4.51 #6: Cedarwood oil 8.87 15.00 Virginian #7: Pine oilSiberian 43.93 48.08 #8: Lavender oil 14.94 24.59 #9: Petitgrain oil10.24 21.23Dosing/Treatment of Non-Citrus Essential Oils with AKG-DiTMEEA

Treated Added Untreated AKG Appearance of Total Total TMEEA TreatedCompared Essential oils Volume Volume disalt to Untreated Sample #1:Basil 10 mL 10 mL 0.2 mL Slight haziness, oil no color change #2:Coriander 10 mL 10 mL 0.2 mL Clear, from colorless oil to slightlyyellow #3: Patchouli 10 mL 10 mL 0.2 mL Slight haziness, oil no colorchange #4: Star Anise 10 mL 10 mL 0.2 mL Slight haziness, oil no colorchange #5: Cinnamon 10 mL 10 mL 0.2 mL Clear, no color change leaf oil#6: Cedarwood 10 mL 10 mL 0.2 mL Slight haziness, from oil, Virginiancolorless to slightly yellow #7: Pine oil,  5 mL  5 mL 0.2 mL Clear,from colorless Siberian to slightly yellow  5 mL 0.4 mL Clear, fromcolorless to slightly yellow #8: Lavender 10 mL 10 mL 0.2 mL Clear, fromcolorless oil to slightly yellow #9: Petitgrain 10 mL 10 mL 0.2 mLClear, same color oil

AKG-DiTMEEA Treatment (4 Days) of Non-Citrus Essential Oils

POV (mmol/L) POV (mmol/L) of Untreated of Treated % Reduction Oil TypeOil Oil in POV Basil Oil 23.88 2.49 89.6 Coriander Oil 23.60 2.44 89.7Patchouli Oil 4.89 0.00 100.0 Star Anise Oil 3.52 0.38 89.2 CinnamonLeaf Oil 4.51 0.57 87.5 Cedarwood Oil, 15.00 0.72 95.2 Virginian PineOil, Siberian 48.08 24.8 48.4 (x2 Treatment Level) Pine Oil, Siberian48.08 15.21 68.4 (x4 Treatment Level) Lavender Oil 24.59 5.83 76.3Petitgrain Oil 21.23 4.28 79.9

Publications cited throughout this document are hereby incorporated byreference in their entirety. Although the various aspects of theinvention have been illustrated above by reference to examples andpreferred embodiments, it will be appreciated that the scope of theinvention is defined not by the foregoing description but by thefollowing claims properly construed under principles of patent law.

1. A method, wherein the method reduces the POV of a perfume, body careproduct, cosmetic product, homecare product, perfumery raw material,flavored article, or food raw material, the method comprising: a. addingan α-oxocarboxylic acid to the perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material having a first POV level; and b. mixing theα-oxocarboxylic acid into the perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material for a time sufficient to reduce the first POV level toa pre-determined second lower level.
 2. A method, wherein the methodreduces, prevents, or ameiorates formulated perfume, body care product,homecare product, cosmetic product, or perfumery raw material-inducedskin irritation of a subject in need thereof, the method comprising: a.adding an α-oxocarboxylic acid to formulated perfume, body care product,homecare product, cosmetic product, or perfumery raw material having afirst POV level; and b. mixing the α-oxocarboxylic acid into theformulated perfume, body care product, homecare product, cosmeticproduct, or perfumery raw material for a time sufficient to reduce thefirst POV level to a pre-determined second lower level, wherein thepre-determined second lower level is sufficient to reduce, prevent, orameliorate the formulated perfume, body care product, homecare product,cosmetic product, or perfumery raw material-induced skin irritation ofthe subject.
 3. The method of claim 1, wherein the perfumery rawmaterial is treated prior to the incorporation into a perfume.
 4. Themethod of claim 1, wherein the perfumery raw material is treated afterincorporation into a perfume.
 5. The method of claim 1, wherein the foodraw material is treated prior to the incorporation into a flavoredarticle.
 6. The method of claim 1, wherein the food raw material isincorporated after the incorporation into a flavored article.
 7. Themethod of claim 1, wherein the concentration of the α-oxocarboxylic acidranges from 0.001 to 10 weight percent, after the addition to theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw material.8. The method of claim 1, wherein the α-oxocarboxylic acid is selectedfrom the group consisting of: pyruvic acid, 2-oxovaleric acid,phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid,oxaloacetic acid, α-ketoglutaric acid, 2-oxopentandioate,indole-3-pyruvic acid, 2-thiopheneglyoxylic acid, trimethylpyruvic acid,2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid,2-oxooctanoic acid, and mixtures thereof.
 9. The method of claim 1,wherein the pre-determined second lower level is between 5 and 20mmol/L.
 10. The method of claim 1, wherein the pre-determined secondlower level is between 0 and 6 mmol/L.
 11. The method of claim 1,further comprising removing the α-oxocarboxylic acid from the formulatedperfume, body care product, cosmetic product, homecare product,perfumery raw material, flavored article, or food raw material havingthe pre-determined second lower level.
 12. The method of claim 11,wherein the step of removing the α-oxocarboxylic acid from theformulated perfume, body care product, cosmetic product, homecareproduct, perfumery raw material, flavored article, or food raw materialcomprises a liquid-liquid extraction.
 13. The method of claim 1, furthercomprising treating the formulated perfume, body care product, cosmeticproduct, homecare product, perfumery raw material, flavored article, orfood raw material with a carbonate salt after removing theα-oxocarboxylic acid to reduce the acidity of the formulated perfume,body care product, perfumery raw material, flavored article, or food rawmaterial.